KR20110077883A - Catalysts for poly(1-butene) and preparation of poly(1-butene) using the same - Google Patents

Abstract

PURPOSE: A catalyst for preparing poly(1-butene) and a method for preparing poly(1-butene) using the same are provided to control mutual reaction between co-catalysts and transition metal oxides having a phenyl group as a substituent. CONSTITUTION: A catalyst for preparing poly(1-butene) comprises (A) transition metal oxides represented by chemical formula I and (B) a cocatalyst compound selected from the group consisting of an aluminoxane compound represented by chemical formula III-1 and an organic aluminum compound represented by chemical formula III-2. In chemical formula I, M is selected from the group consisting of Group 3~10 elements on the periodic table; and Cp^1 and Cp^2 are a ligand having a cyclopentadienyl skeleton.

Description

Catalyst for preparing poly (1-butene) and method for preparing poly (1-butene) using same {Catalysts for poly (1-butene) and preparation of poly (1-butene) using the same}

The present invention relates to a catalyst used to prepare poly (1-butene).

Poly (1-butenes) prepared using Ziegler-Natta catalysts are mainly isotactic poly (1-butene), and with metallocene catalysts, syndiotactic poly (1 Syndiotactic Poly (1-butene) and Atactic Poly (1-butene) are also available, but currently commercially produced poly (1-butene) is mainly Ziegler- It is prepared from Nata catalyst.

Metallocene catalysts allow the production of poly (1-butenes) and poly (1-butenes) of different physical properties made from Ziegler-Natta catalysts, but poly (1-butenes) having molecular weights applicable to commercial products. To this end, a complex metallocene catalyst is required.

However, in order to synthesize such a complex metallocene catalyst compound, a complex synthesis process and apparatus of several steps are required, and thus, a major factor that increases the manufacturing cost of poly (1-butene) products produced using the metallocene catalyst is required. This has been one of the obstacles to the expansion of the poly (1-butene) market using metallocene catalysts.

In this regard, KR 2005-0127244 polymerized poly (1-butene) using a catalyst based on titanium (Ti), but this catalyst was prepared using a conventional Ziegler-Natta catalyst. (1-butene) is polymerized.

In addition, WO 2004/050724 polymerizes poly (1-butene) using a metallocene catalyst and Me ₂ Si (2-Me-5,6 [tetramethylcyclotrimethylen] Ind) ₂ ZrCl ₂ . Ansa type metallocene catalyst with a complex structure is used.

Accordingly, methods for producing low molecular weight, high molecular weight poly (1-butenes) have become a major concern of all research groups and companies around the world.

The present invention for solving the above problems is to provide a metallocene catalyst for producing poly (1-butene) containing a novel metallocene (Metallocene) catalyst compound.

Another object of the present invention is to provide a method for producing poly (1-butene) using the poly (1-butene) production catalyst and a poly (1-butene) prepared according to the method.

The present invention to achieve the above object,

(A) a transition metal compound represented by the following [Formula I]; And

Formula I

In [Formula I], M is selected from the group consisting of Group 3-10 elements on the periodic table, and Cp ¹ and Cp ² are ligands each having a cyclopentadienyl skeleton, and are represented by the following Chemical Formula II-1 and Chemical Formula II -2] having one or more substituents selected from the group consisting of

 [Formula II-1]

[Formula II-2]

In [Formula II-1] and [Formula II-2],

Z is an element of group 15 or 16 of the periodic table,

R is hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, and a silylalkyl having 1 to 20 carbon atoms ), C6-C20 aryl (Aryl), C7-C20 arylalkyl, C7-C20 alkylaryl, C6-C20 arylsilyl and It is selected from the group consisting of silylaryl group having 6 to 20 carbon atoms,

m is 1 or 2 depending on the type of Z,

p is an integer within the range 1-5,

Other substituents bonded to Cp ¹ and Cp ² in addition to the substituents represented by [Formula II-1] and [Formula II-2], and ZRm of [Formula II-1] and [Formula II-2] Other substituents bonded to carbon atoms in the unsubstituted phenyl ring are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkylsilyl having 1 to 20 carbon atoms Group, C1-C20 silylalkyl group, C1-C20 haloalkyl group, C6-C20 aryl group, C7-C20 arylalkyl group, C2-C20 It may be an alkylaryl group, an arylsilyl group having 6 to 20 carbon atoms, a silylaryl group having 6 to 20 carbon atoms, or a halogen group, and these substituents may be bonded to each other by a ring. Can form a

In [Formula I], X is an alkyl group having 1 to 20 carbon atoms (Alky),

C3-C20 cycloalkyl group, C1-C20 alkylsilyl group, C1-C20 silylalkyl group, C6-C20 aryl group, C7-C20 20 arylalkyl groups, 7 to 20 carbon atoms, 6 to 20 carbon atoms, 6 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms Alkoxy group, C1-C20 Alkylsiloxy group, C6-C20 aryloxy group, Halogen group, Amine group and Tetrahydroborate group Selected from the group consisting of,

n is an integer in the range of 1 to 5, depending on the central metal.

(B) a catalyst for producing poly (1-butene) comprising a co-catalyst compound selected from the group consisting of an aluminoxane compound represented by the following [Formula III-1] and an organoaluminum compound represented by the following [Formula III-2] to provide.

[Formula III-1]

(In [Formula III-1], R ¹ is an alkyl group having 1 to 10 carbon atoms, q is an integer within the range of 1 to 70.)

[Formula III-2]

(In [Formula III-2], R ² , R ³ , R ⁴ are the same as or different from each other, each having 1 to 10 alkyl groups, 1 to 10 alkoxy groups, or halogen groups, R ² , R At least one of ³ and R ⁴ is an alkyl group having 1 to 10 carbon atoms)

In addition, the present invention is poly (1-butene), characterized in that in the presence of the above-mentioned catalyst for producing poly (1-butene), 1-butene is homopolymerized or copolymerized with a compound containing a double bond and 1-butene. It provides a method of manufacturing.

The present invention also provides a poly (1-butene) prepared according to the method for producing a poly (1-butene).

According to the present invention as described above, the interaction between the metallocene catalyst compound and the cocatalyst without using an Ansa Type metallocene catalyst of a complex structure in a homogeneous or heterogeneous phase It is possible to provide a catalyst for producing poly (1-butene) that can adjust the degree of physical properties of the poly (1-butene).

Hereinafter, the present invention as described above will be described in more detail.

<Catalyst for producing poly (1-butene)>

The catalyst for producing poly (1-butene) according to the present invention includes (A) a transition metal compound represented by the above [Formula I] as the main catalyst, and (B) an aluminoxane compound represented by the above [Formula III-1]; It includes a cocatalyst compound selected from the group consisting of an organoaluminum compound represented by the formula (III-2), the cocatalyst is such that the main catalyst has a polymerization catalyst activity.

The present invention is a complex catalyst comprising a main catalyst and a cocatalyst, wherein the main metal transition metal compound has a phenyl group containing a hetero atom as a substituent, and the present invention provides a transition metal compound and a promoter as described above. By controlling the degree of interaction between the two, the physical properties (molecular weight and / or melting point) of the poly (1-butene) to be produced can be controlled.

That is, in the catalyst of the present invention, the cocatalyst is characterized in that it can react with the main catalyst to control the stereoregularity of the poly (1-butene) polymer. Specifically, at least one substituent selected from the group consisting of [Formula II-1] and [Formula II-2] in the transition metal compound represented by the above [Formula I] is an alumina represented by the above [Formula III-1] By reacting with a compound selected from the group consisting of a noxane compound and an organoaluminum compound represented by the above [Formula III-2], poly (1-butene) is determined by determining the direction of insertion of poly (1-butene) with respect to the catalytic active point. Butenes) can be adjusted.

In the conventional general metallocene catalyst for producing poly (1-butene), the Cp ¹ and Cp ² functional groups of Formula 1 are connected by a compound containing carbon (C) or a functional group containing silicon (Si) (WO2004). See transition metal compound in / 050724). However, the compound having such a functional group has a disadvantage in that the production of the catalyst is difficult, and the yield of the prepared catalyst is also low. On the contrary, since the compound according to the present invention does not have such a functional group, the preparation of the catalyst is easy and the yield of the prepared catalyst is also increased.

In addition, as described above, the present invention can control the stereoregularity of poly (1-butene), thereby producing a poly (1-butene) having a high molecular weight through the product having excellent mechanical strength (for example, pipe products). In addition, poly (1-butene) having a wide molecular weight distribution may be prepared to improve workability in forming a product.

Such a catalyst of the present invention will be described in detail for each component as follows.

1) a transition metal compound represented by the above [Formula I]

M in [Formula I] is selected from the group consisting of Group 3 to 10 elements on the periodic table, preferably a Group 4 element on the periodic table with high activity, non-limiting examples of zirconium (Zr), titanium (Ti ) Or hafnium (Hf).

In addition, Cp ¹ and Cp ² of [Formula I] are a ligand having a cyclopentadienyl skeleton (Ligand), cyclopentadienyl (Cyclopentadienyl) group, Indenyl group, or fluorenyl (Fluorenyl) And the like, and have at least one substituent represented by the following [Formula II-1] and / or [Formula II-2].

 [Formula II-1]

[Formula II-2]

In [Formula II-1] and [Formula II-2], the hexagonal ring structure represents a phenyl ring, Z is an element of group 15 or 16 on the periodic table, and R is hydrogen or carbon number 1-20 alkyl (alkyl) groups, 3-20 carbonylcycloalkyl groups, 1-20 carbonylsilyl groups, 1-20 carbonyl silylalkyl groups, 6-20 carbon atoms Aryl (Aryl) group, C7-20 arylalkyl group, C7-20 alkylaryl group, C6-C20 arylsilyl group and C6-C20 silylaryl It may be selected from the group consisting of (Silylaryl) group, m is depending on the type of Z, 1 or 2, p may have a value of 1-5.

Specifically, Z is an element of group 15 or 16 on the periodic table, preferably nitrogen (Nitrogen, N), phosphorus (Phosphorus, P), arsenic (Arsenic, As), oxygen (Oxygen, O), sulfur (Sulfur, S) and atoms of selenium (Selenium, Se).

In addition, the C 1-20 alkyl (Alky), C 3-20 cycloalkyl, C 1-20 alkylsilyl, C 1-20 silylalkyl Non-limiting examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group (Octyl) group, nonyl group, decyl group, cyclopropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group, cyclooctyl (Cyclooctyl) Group, decahydronaphthalyl group, methylsilyl group, dimethylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group (Triethylsilyl), Propylsilyl, Dipropylsilyl, Dipropylsilyl, Tributylsilyl, Butylsilyl, Dibu Dibutylsilyl group, Tributylsilyl group, (methylsilyl) methyl ((Methylsilyl) methyl) group, (dimethylsilyl) methyl ((Dimethylsilyl) methyl), (trimethylsilyl) methyl ((Trimethylsilyl) methyl ), (Ethylsilyl) methyl ((Ethylsilyl) methyl) group, (diethylsilyl) methyl ((Dethylsilyl) methyl) group, (triethylsilyl) methyl ((Triethylsilyl) methyl) group, (methylsilyl) ethyl ( (Methylsilyl) ethyl), (dimethylsilyl) ethyl ((Dimethylsilyl) ethyl) group, (trimethylsilyl) ethyl ((Trimethylsilyl) ethyl) group, etc.

C 6-20 aryl (Aryl) group, C7-20 arylalkyl (Arylalkyl) group, C7-20 alkylaryl (Alkylaryl) group, C6-C20 arylsilyl (Arylsilyl) group and Non-limiting examples of silylaryl groups having 6 to 20 carbon atoms include phenyl group, biphenyl group, terphenyl group, naphtyl group, and fluorenyl group. Group, Benzyl Group, Phenylethyl, Phenylpropyl Group, Methylphenyl Group, Dimethylphenyl Group, Trimethylphenyl Group, Ethylphenyl Group, Diethyl Diphenylphenyl group, Triethylphenyl group, Propylphenyl group, Dipropylphenyl group, Tripropylphenyl group, Phenylsilyl group, Methylphenylsilyl group Dimethylphenylsilyl Group, Methyl Diphenyl Silyl, Triphenylsilyl lsilyl), ethylphenylsilyl (Ethylphenylsilyl), (methylphenyl) silyl ((Methylphenyl) silyl), (ethylphenyl) silyl ((Ethylphenyl) silyl) trifluoromethylphenylsilyl (Trifluoromethylphenylsilyl), (methylsilyl (Phenyl) ((Methylsilyl) phenyl) group, (dimethylsilyl) phenyl ((Dimethylsilyl) phenyl) group, (trimethylsilyl) phenyl ((Trimethylsilyl) phenyl) group, (ethylsilyl) phenyl ((Ethylsilyl) phenyl) group (di Ethylsilyl) phenyl ((Diethylsilyl) phenyl) group, (triethylsilyl) phenyl ((Triethylsilyl) phenyl) group, propylsilylphenyl ((Propylsilyl) phenyl) group, dipropylsilylphenyl ((Dipropylsilyl) phenyl) group, butyl Silylphenyl ((Butylsilyl) phenyl) groups, dibutylsilylphenyl ((Dibutylsilyl) phenyl) groups and the like.

Meanwhile, in addition to the substituents represented by the above [Formula II-1] and [Formula II-2], other substituents bonded to Cp ¹ and Cp ² and the combination with ZRm of the above [Formula II-1] and [Formula II-2] Other substituents bonded to carbon atoms in the unsubstituted phenyl ring are hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkylsilyl having 1 to 20 carbon atoms Group, C1-C20 silylalkyl group, C1-C20 haloalkyl group, C6-C20 aryl group, C7-C20 arylalkyl group, C2-C20 It may be an alkylaryl group, an arylsilyl group having 6 to 20 carbon atoms, a silylaryl group having 6 to 20 carbon atoms, or a halogen group, and these substituents may be bonded to each other by a ring. May be formed.

In this case, in addition to the substituents represented by [Formula II-1] and [Formula II-2], other substituents bonded to Cp ¹ and Cp ² and not bonded to ZRm of [Formula II-1] and [Formula II-2] As another substituent bonded to a carbon atom in the phenyl ring, an alkyl group having 1 to 20 carbon atoms,

Non-limiting examples of cycloalkyl groups having 3 to 20 carbon atoms, alkylsilyl groups having 1 to 20 carbon atoms, silylalkyl groups having 1 to 20 carbon atoms, and haloalkyl groups having 1 to 20 carbon atoms include methyl groups. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl (Decyl) group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclolooctyl group, decahydronaphthalyl group, methyl Methylsilyl group, dimethylsilyl group, trimethylsilyl group, trimethylsilyl group, ethylsilyl group, diethylsilyl group, triethylsilyl group, triethylsilyl group, propylsilyl group, Dipropylsilyl group, Tripropylsilyl group, Butylsilyl group, Dibutylsilyl group, Tributylsilyl group, (methylsilyl) methyl ((Methylsilyl) methyl) group, (dimethylsilyl) methyl ((dimethylmethylyl) methyl) group, (trimethylsilyl) methyl ((trimethylsilyl) methyl) group, (ethylsilyl ) (Ethylsilyl) methyl), (diethylsilyl) methyl ((Dethylsilyl) methyl), (triethylsilyl) methyl ((Triethylsilyl) methyl) group, (methylsilyl) ethyl ((Methylsilyl) ethyl) group , (Dimethylsilyl) ethyl ((Dimethylsilyl) ethyl) group, (trimethylsilyl) ethyl ((Trimethylsilyl) ethyl) group, trifluoromethyl group, trichloromethyl group, etc.,

Aryl (Aryl) group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms, Alkylaryl group having 7 to 20 carbon atoms, arylsilyl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms Non-limiting examples of 20 silylaryl groups include phenyl, biphenyl, terphenyl, naphtyl, fluorenyl and benzyl. (Benzyl) group, Phenylethyl, Phenylpropyl group, Methylphenyl group, Dimethylphenyl group, Trimethylphenyl group, Ethylphenyl group, Diethylphenyl ), Triethylphenyl group, Propylphenyl group, Dipropylphenyl group, Tripropylphenyl group, Phenylsilyl group, Methylphenylsilyl group Methylphenylsilyl group Dimethylphenylsilyl (Dimethylphenylsilyl), methyldiphenylsilyl, triphenylsilyl, Ethylphenylsilyl (Ethylphenylsilyl), (Methylphenyl) silyl ((Methylphenyl) silyl), (Ethylphenyl) silyl ((Ethylphenyl) silyl) Trifluoromethylphenylsilyl (Trifluoromethylphenylsilyl), (Methylsilyl) phenyl ((Methylsilyl ) phenyl) group, (dimethylsilyl) phenyl ((Dimethylsilyl) phenyl) group, (trimethylsilyl) phenyl ((Trimethylsilyl) phenyl) group, (ethylsilyl) phenyl ((Ethylsilyl) phenyl) group (diethylsilyl) phenyl ( (Diethylsilyl) phenyl), (triethylsilyl) phenyl ((Triethylsilyl) phenyl) group, propylsilylphenyl ((Propylsilyl) phenyl) group, dipropylsilylphenyl ((Dipropylsilyl) phenyl) group, butylsilylphenyl ((Butylsilyl ) phenyl) group, dibutylsilylphenyl ((Dibutylsilyl) phenyl) group,

The halogen group includes a fluoro group, a chloro group, a bromo group, an iodo group, and the like.

Meanwhile, in [Formula I], X is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms. Silylalkyl group, C6-C20 aryl (Aryl) group, C7-C20 arylalkyl, C7-C20 alkylaryl, C6-C20 arylsilyl ( Arylsilyl group and C6-C20 silylaryl group, C1-C20 alkoxy group, C1-C20 alkylsiloxy group, C6-C20 aryloxy It may be a group, a halogen (Halogen) group, an amine (Amine) group, a tetrahydroborate group, n is an integer of 1 to 5 can be determined to vary depending on the oxidation number of the central metal.

At this time, the C1-20 alkyl (Alky) group, C3-20 cycloalkyl group, C1-C20 alkylsilyl group, C1-C20 which are available as X of [Formula I] Non-limiting examples of silylalkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Heptyl, Octyl, Nonyl, Decyl, Cycylpropyl, Cyclobutyl, Cyclopentyl, Cyclohexyl , Cyclooctyl group, decahydronaphthalyl group, methylsilyl group, dimethylsilyl group, dimethylsilyl group, trimethylsilyl group, ethylsilyl group, ethylsilyl group, diethylsilyl group Diethylsilyl group, Triethylsilyl group, Propylsilyl group, Dipropylsilyl group, Tripropylsilyl group, Butyl Butylsilyl group, Dibutylsilyl group, Tributylsilyl group, Tributylsilyl group, (methylsilyl) methyl ((Methylsilyl) methyl group, (dimethylsilyl) methyl ((Dimethylsilyl) methyl) group, (trimethyl (Sylyl) methyl ((Trimethylsilyl) methyl) group, (ethylsilyl) methyl ((Ethylsilyl) methyl) group, (diethylsilyl) methyl ((Dethylsilyl) methyl) group, (triethylsilyl) methyl ((Triethylsilyl) methyl) Groups, (methylsilyl) ethyl ((Methylsilyl) ethyl), (dimethylsilyl) ethyl ((Dimethylsilyl) ethyl), (trimethylsilyl) ethyl ((Trimethylsilyl) ethyl), etc.

An aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylsilyl group having 6 to 20 carbon atoms, and Non-limiting examples of silylaryl groups having 6 to 20 carbon atoms include phenyl group, biphenyl group, terphenyl group, naphtyl group, and fluorenyl group. Group, Benzyl Group, Phenylethyl, Phenylpropyl Group, Methylphenyl Group, Dimethylphenyl Group, Trimethylphenyl Group, Ethylphenyl Group, Diethyl Diphenylphenyl group, Triethylphenyl group, Propylphenyl group, Dipropylphenyl group, Tripropylphenyl group, Phenylsilyl group, Methylphenylsilyl group Dimethylphenylsilyl group, methyldiphenylsilyl, triphenylsilyl (Trip henylsilyl group, ethylphenylsilyl group, (methylphenyl) silyl ((Methylphenyl) silyl group, (ethylphenyl) silyl ((Ethylphenyl) silyl group, trifluoromethylphenylsilyl) group, (methylsilyl) Phenyl ((Methylsilyl) phenyl) group, (dimethylsilyl) phenyl ((Dimethylsilyl) phenyl) group, (trimethylsilyl) phenyl ((Trimethylsilyl) phenyl) group, (ethylsilyl) phenyl ((Ethylsilyl) phenyl) group (diethyl Silyl) phenyl ((Diethylsilyl) phenyl) group, (triethylsilyl) phenyl ((Triethylsilyl) phenyl) group, propylsilylphenyl ((Propylsilyl) phenyl) group, dipropylsilylphenyl ((Dipropylsilyl) phenyl) group, butylsilyl Phenyl ((Butylsilyl) phenyl) group, dibutylsilylphenyl ((Dibutylsilyl) phenyl) group, and the like,

Non-limiting examples of an alkoxy group having 1 to 20 carbon atoms and an alkylsiloxy group having 1 to 20 carbon atoms as X include a methoxy group, an ethoxy group, and a propoxy group. ), Butoxy group, pentoxy group, hexyloxy group, methylsiloxy group, dimethylsiloxy group. Trimethylsiloxy group, ethylsiloxy group, diethylsiloxy group, triethylsiloxy group and the like,

Aryloxy groups having 6 to 20 carbon atoms as X include phenoxy groups, naphtoxy groups, methylphenoxy groups, dimethylphenoxy groups, and trimethylphenoxy. ), Ethylphenoxy group, diethylphenoxy group, triethylphenoxy group, propylphenoxy group, dipropylphenoxy group, dipropylphenoxy group, tripropylphenoxy group (Tripropylphenoxy) group, etc.

Halogen groups available as X include a fluoro group, a chloro group, a bromo group, an iodo group, and the like.

The amine groups available for X include dimethylamine, diethylamine, dipropylamine, dibutylamine, diphenylamine and dibenzylamine. (Dibenzylamine) group, and the like.

Herein, X in [Formula I] is a methyl group, an ethyl group, a propyl group, a phenoxy group, a naphtoxy group, a methylphenoxy group, Dimethylphenoxy group, Trimethylphenoxy group, Ethylphenoxy group, Diethylphenoxy group, Triethylphenoxy group, Propylphenoxy group, Dipropylphenoxy, Tripropylphenoxy group, Chloro group, Bromo group, Dimethylamine group, Diethylamine group, Dipropylamine ), Dibutylamine, Diphenylamine group, Dibenzylamine group, and tetrahydroborate group are preferable because of the high possibility of synthesis and excellent activity compared to other functional groups.

2) The aluminoxane compound represented by the above [Formula III-1] and / or the organoaluminum compound represented by the above [Formula III-2]

In the catalyst of the present invention, (B) the aluminoxane compound represented by the above [Formula III-1] and / or the organoaluminum compound represented by the above [Formula III-2] is represented by the above (A) [Formula I] Along with the role of the cocatalyst compound which causes the transition metal compound to have a polymerization catalyst activity, it may play a role of controlling the stereoregularity of poly (1-butene) by reacting with the transition metal compound represented by the above [Formula I]. have.

In the present invention, in the case of the aluminoxane compound of [Formula III-1], it may have a linear, cyclic or network structure, non-limiting examples of methylaluminoxane (Methylaluminoxane) , Ethyl aluminoxane (Ethylaluminoxane), butyl aluminoxane (Butylaluminoxane), hexyl aluminoxane (Hexylaluminoxane), and octyl aluminoxane (Octylaluminoxane), decyl aluminoxane (Decylaluminoxane).

In addition, the organoaluminum compound represented by [Formula III-2] is trimethylaluminum (Trimethylaluminum), triethylaluminum (Triethylaluminum), tributylaluminum, Trihexylaluminum, Trioctyl aluminum (Trioctylaluminum) Trialkylaluminum such as tridecylaluminum; Dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum methoxide, and dibutylaluminum methoxide; Dialkylaluminum alkoxides such as dimethylaluminum chloride, diethylaluminum chloride, and dibutylaluminum chloride; Alkyl aluminum dialkoxides such as methylaluminum dimethoxide, ethylaluminum dimethoxide, and butylaluminum dimethoxide; And alkylaluminum dihalide such as methylaluminum dichloride, ethylaluminum dichloride, and butylaluminum dichloride.

In this case, the [Chemical Formula III-1] and [Chemical Formula III-2], which are cocatalyst compounds of the present invention, are not limited to the above examples, and may be used singly or in combination of two or more.

Meanwhile, the catalyst for preparing poly (1-butene) of the present invention may be used by being supported on an inorganic or organic compound. In this case, the carrier is not limited to a specific material but fine pores on the surface thereof. If it has a large surface area, any one is fine.

Specifically, non-limiting examples of inorganic compounds that can be used as a carrier include silica, alumina, bauxite, zeolite, MgCl ₂ , CaCl ₂ , MgO, ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , or mixtures thereof (eg SiO ₂ -MgO, SiO ₂ -Al ₂ O ₃ , SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O _{5 , SiO 2 -CrO 3, SiO 2} -TiO 2 -MgO) and the like, in this case, the inorganic compound may also include a small amount of carbonate (carbonate), sulfate (sulfate), nitrate (nitrate). Non-limiting examples of organic compounds that can be used as a carrier include Starch, Cyclodextrin, synthetic polymers, and the like.

Here, in the case where the catalyst for preparing poly (1-butene) of the present invention is supported on an inorganic or organic compound, a method of directly supporting the transition metal compound (A) on a carrier dehydrated, the carrier is an organic aluminoxane compound. Pretreatment with (B) or organoaluminum compound (B), followed by supporting the transition metal compound (A), the support of the transition metal compound (A) on a carrier followed by organoaluminoxane compound (B) or organoaluminum compound (B ), A method of reacting a transition metal compound (A) with an organoaluminoxane compound (B) or an organoaluminum compound (B) to make the transition metal compound catalytically active, followed by reaction with a carrier. .

Solvents used to support the catalyst for producing poly (1-butene) of the present invention include pentane, hexane, heptane, octane, nonane, decane, and undecylenate. Aliphatic hydrocarbon solvents such as Undecane and Dodecane; Aromatic hydrocarbon solvents such as benzene, chlorobenzene, dichlorobenzene, trichlorobenzene, and toluene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, dichloroethane, and trichloroethane, and the like, and these solvents may be used alone or in combination of two or more thereof. .

The amount of the transition metal compound (A) and (B) organoaluminoxane compound (B) or organoaluminum compound (B) used when supporting the catalyst for producing poly (1-butene) of the present invention is not particularly limited, The molar ratio of B) / (A) is 1/1 to 10000/1, and specifically, it is preferably used at a ratio of 1/1 to 2000/1.

On the other hand, the temperature maintained when supporting the catalyst for producing poly (1-butene) of the present invention is -50 to 150 ° C, specifically -20 to 100 ° C.

<Poly (1-butene) and preparation method thereof>

In the present invention, 1-butene is polymerized, specifically 1-butene is polymerized, or a compound containing a double bond is copolymerized with 1-butene using the catalyst configuration described in <Catalyst for preparing poly (1-butene)>. It is possible to provide a method for producing a poly (1-butene) comprising.

Accordingly, poly (1-butene) prepared by polymerizing 1-butene in the presence of a catalyst for producing poly (1-butene) of the present invention may be selected from the group consisting of poly (1-butene) homopolymers; Or a copolymer of 1-butene with a compound containing a double bond. That is, in the present invention, copolymerization of a compound containing a double bond with 1-butene can be carried out using a catalyst for producing poly (1-butene) according to the present invention. In addition, the poly (1-butene), preferably poly (1-butene) copolymer of the present invention may contain the catalyst for producing poly (1-butene) according to the present invention inside a polymer.

As described above, when preparing poly (1-butene) using the catalyst for producing poly (1-butene) of the present invention, poly (1-butene) has a high molecular weight and melting point due to the interaction between the main catalyst and the promoter, and has a high stereoregularity. 1-butene) can be obtained. In addition, the stereoregularity of the poly (1-butene) may also be adjusted according to the structure of the catalyst for producing poly (1-butene) and polymerization conditions. That is, the physical properties of the poly (1-butene) to be polymerized by controlling the polymerization temperature, the concentration of 1-butene, the amount of catalyst, and the like can be controlled.

Here, the compound containing the double bond used in the preparation of the copolymer according to the present invention may be other butenes or other monomers other than 1-butene.

On the other hand, in the case of producing poly (1-butene) using the catalyst for producing poly (1-butene) of the present invention, the polymerization is carried out in a slurry phase, a liquid phase, a gas phase, a bulk. (Bulk Phase) can be carried out. If the polymerization is carried out in the liquid or slurry phase, a solvent or olefin (specifically 1-butene) itself may be used as the medium.

The solvent used in the polymerization reaction is not particularly limited, but non-limiting examples include butane, pentane, hexane, heptane, octane, nonane, decane and decane. Aliphatic hydrocarbon solvents such as Undecane, Dodecane, Dodecane, Cyclopentane, Methylcyclopentane, and Cyclohexane; Aromatic hydrocarbon solvents such as benzene, chlorobenzene, dichlorobenzene, trichlorobenzene, toluene, and xylene; Halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane and trihloroethane, and the like. It may be used by mixing in a constant ratio.

In the practice of the polymerization through the slurry of the present invention, liquid phase, gas phase, bulk process, being the amount of the transition metal compound (A) is used particularly limited, 10 to the central metal concentration in the reaction system used in the ^{polymerization 10} to 1 mol / liter is suitable, ideally 10 ^-8 to 10 ^-2 mol / liter. If the amount of the transition metal compound is used below the above-mentioned concentration, the produced catalytic activity may not be expressed. When the amount of the transition metal compound is used above the above-mentioned concentration, the exothermicity is increased during the production of the poly (1-butene). It may be impossible.

The amount of the aluminoxane compound (B) or the organoaluminum compound (B) used in the polymerization of the present invention is not particularly limited, the molar ratio of (B) / (A) used in the reaction system was 1/1 and 10 ^6/1 It is preferably used in a ratio of ^{1/1 ~ 5x10 4/1} . If the aluminoxane compound (B) or the organoaluminum compound (B) is used in an amount less than the above ratio, the polymerization activity may be insufficient, and if the aluminoxane compound (B) or the organoaluminum compound (B) is used in excess of the above ratio, it may not be possible to control the production reaction of the poly (1-butene). Because.

In addition, when manufacturing poly (1-butene) using the catalyst for poly (1-butene) manufacture of this invention, although polymerization temperature is not specifically limited, It is -50-200 degreeC, specifically, it is 0-150 degreeC. desirable. In addition, the polymerization reaction can be batch, semi-continuous or continuous type, the polymerization pressure is 1 to 3000 atm, specifically 1 to 500 atm. Do.

On the other hand, the weight average molecular weight (M _w ) of the poly (1-butene) obtained in accordance with the present invention is 5,000 to 2,000,000, preferably 20,000 to 2,000,000, the molecular weight distribution (MwD, weight average molecular weight (Mw) / number average molecular weight ( Mn)) is 3-30, Preferably it is 5-25. That is, poly (1-butene) prepared by the catalyst for producing poly (1-butene) of the present invention may have a wide molecular weight distribution of 3 to 30. Thus, when the molecular weight distribution of the poly (1-butene) is wide, The processing of the product is easy and the field of application can also provide a variety of poly (1-butene).

Hereinafter, the present invention will be described in more detail with reference to synthesis examples and polymerization examples, but the scope of the invention is not limited to the following.

Synthesis Example of Transition Metal Compound

All synthesis reactions were carried out in an Inert Atmosphere such as Nitrogen or Argon, using standard Schlenk technology and Glove Box technology. Solvent required for synthesis was used to remove water by passing through an activated alumina column and then stored on an activated molecular sieve (Molecular Sieve 5A, Yakuri Pure Chemicals Co). the double substitution of hydrogen used in the structure analysis chloroform (Chloroform- d, CDCl ₃₎ was used as dried over molecular sieve (Molecular sieve 5A, Yakuri Pure Chemicals Co) after activation purchased from Cambridge Isotope Laboratories Corporation.

Reagents used for the synthesis were purchased and used without further purification, and reagents not available for purchase were synthesized using the synthesis methods described in the literature.

¹ H NMR and ¹³ C NMR were measured using a Bruker Avance 400 Spectrometer at room temperature, and the chemical shift of the NMR spectrum was determined by the chemical shift ( ¹ H NMR) indicated by deuterated chloroform (CDCl ₃ ). In the case of δ = 7.24 ppm, and ¹³ C NMR, δ = 77.0 ppm). All elemental analyzes were measured using EA 1110-FISION (CE Instruments).

Synthesis Example 1

Bis [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 1-1 1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( p Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

4-Bromo- N, N -dimethylaniline (4.00 g, 20 mmol) is dissolved in 50 ml of diethyl ether and then 1 equivalent of normal butyllithium (8.0 mL) is added at 0 ° C. After stirring at room temperature for 2 hours, the solvent was evaporated and the obtained lithium salt was washed twice with normal hexane and dried in vacuo. The lithium salt was re-dissolved in 40 ml of tetrahydrofuran at -78 ° C, and 20 ml of an equivalent amount of 3,4-dimethylsiglopenta-2-enone (2.20 g, 20 mmol) was dissolved in cannula. After dropping through, slowly raised to room temperature and stirred overnight. The reaction was terminated by adding an appropriate amount of saturated aqueous ammonium chloride solution to the orange solution. Then, only the organic layer was extracted with diethyl ether (50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed from the rotary evaporator to obtain a yellow oil. The oil was dissolved in methylene chloride (30 mL), and then para-toluenesulfonic acid hydrate (ca. 0.1 g) was stirred for 1 hour at room temperature. An ivory solid was produced. The solvent was evaporated with a rotary evaporator, precipitated with 30 ml of normal hexane, and filtered using Glass Frit. The filtered solid was washed with ethanol (30 ml), diethyl ether (30 mL), n- pentane (30 mL) and dried in vacuo to give 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene. This was obtained in 63% yield.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.33 (d, 2H), 6.69 (d, 2H), 6.45 (s, 1H), 3.21 (s, 2H), 2.93 (s, 6H), 1.94 (s , 3H), 1.86 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 142.8, 135.4, 133.7, 128.3, 125.5, 112.9, 45.2, 40.8, 13.4, 12.6.

Synthesis Example 1-2

Bis [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1.280 g (6.0 mmol) of 1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadiene synthesized in Synthesis Example 1-1 was dissolved in 30 ml diethyl ether, followed by equivalents of normal at -78 ° C. Butyl lithium (2.4 mL) was added, and then raised to room temperature and stirred for 4 hours. The solvent was evaporated and the white lithium salt obtained was mixed with half equivalent of tetrachlorobis (tetrahydrofuran) zirconium (3.0 mmol, 1.132 g) and dissolved in toluene (50 mL) at -78 ° C. The mixed solution was slowly warmed to room temperature and stirred while heating to 50 ° C. overnight. Then, Celite filtration to remove lithium chloride (LiCl) formed as a reaction by-product and evaporating all the solvents gave 0.968 g of bis- [1- ( p -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride Yield was 55% yield. Also, red crystalline solid can be obtained by recrystallization at -20 ° C with methylene chloride / normal hexane solution.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.34 (d, 4H), 6.77 (d, 4H), 6.14 (s, 4H), 2.99 (s, 12H), 1.77 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 149.7, 127.1, 126.2, 123.9, 121.7, 114.6, 112.6, 40.5, 13.1. Anal. Calcd for C ₃₀ H ₃₆ Cl ₂ N ₂ Zr: C, 61.41; H, 6.18 .; N, 4.77. Found: C, 61.60; H, 6. 25; N, 4.99.

Synthesis Example 2

Bis- [1- ( m -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 2-1

One-( m -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene (1- ( m -Dimethylaminophenyl) -3,4-dimethylcyclopentadiene, ( m -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

3-bromo- N , N -dimethylaniline (4.00 g, 20 mmol) was dissolved in 50 mL of diethyl ether and then 1 equivalent of normal butyllithium (8.0 mL) was added at 0 ° C. After stirring at room temperature for 2 hours, the temperature was lowered to -78 ° C and 20 mL of tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) was added was added dropwise. Slowly put up and stir overnight. Then, distilled water (10 mL) was added to the obtained brown solution, and 20 mL of HCl solution was added thereto. Then, extract and collect only the aqueous layer and wash with 50 mL of diethyl ether. The collected aqueous layer was neutralized again with 10% NaOH aqueous solution, and then the organic layer was extracted with diethyl ether (2 × 50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was evaporated with a rotary evaporator and the yellow oil obtained was purified by column chromatography (silica gel, ethyl acetate / normal hexane = 1/10) to give 1.27 g of a pale yellow solid, 1- ( m -dimethylaminophenyl) -3. , 4-dimethylcyclopentadiene was obtained in 30% yield.

¹ H confirming the synthesis of 1- ( m -dimethylaminophenyl) -3,4-dimethylcyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.17 (t, 1H), 6.86-6.83 (m, 2H), 6.64 (s, 1H), 6.59 (dd, 1H), 3.28 (s, 2H), 2.96 (s, 6H), 1.98 (s, 3H), 1.90 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 150.9, 143.3, 137.1, 135.5, 135.4, 131.4, 129.1, 113.7, 111.0, 108.9, 45.4, 40.7, 13.4, 12.6.

Synthesis Example 2-2

Bis- [1- ( m -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m -Dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m -Me ₂ NC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1- ( m -dimethylaminophenyl) -3,4-dimethylcyclopentadiene (0.853 g, 4.0 mmol) synthesized in Synthesis Example 2-1 was dissolved in 20 mL diethyl ether, and then dried at -78 ° C. One equivalent of normal butyllithium (1.6 mL) was added. The reactor was raised to room temperature and stirred for 4 hours. The solvent was evaporated, and the white lithium salt obtained was mixed with half equivalent of tetrachlorobis (tetrahydrofuran) zirconium (0.755 g, 2 mmol) and dissolved in 30 mL of toluene at -78 ° C. The mixed solution was slowly raised to room temperature and stirred while heating to 60 ° C. overnight. Next, lithium chloride (LiCl) formed as a by-product of the reaction was removed by Celite filtration, and the solvents were all evaporated. Then, the resultant was washed with normal hexane and dried to obtain bis- [1- ( m -dimethylaminophenyl as a light yellow crystalline solid. 0.567 g (48% yield) of 3-3,4-dimethylcyclopentadienyl] zirconium dichloride was obtained. ¹ H confirming the synthesis of the bis- [1- ( m -dimethylaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.29 (t, 2H), 6.81 (d, 2H), 6.77 (s, 2H), 6.66 (d, 2H), 6.21 (s, 4H), 3.00 (s , 12H), 1.82 (s, 12H).

¹³ C {1H} NMR (100.62 MHz, CDCl ₃ ): δ 151.1, 134.3, 129.7, 128.0, 123.5, 116.6, 113.5, 111.6, 109.6, 40.6, 13.3.

Anal. Calcd for C ₃₀ H ₃₆ Cl ₂ N ₂ Zr: C, 61.41; H, 6.18 .; N, 4.77.

Found: C, 62.04; H, 6. 37; N, 4.77.

Synthesis Example 3

Bis [1- (3,5-  N , N , N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5-tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5 -(Me ₂ N) 2C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 3-1

1-bromo-3,5- ( N , N , N ', N'- Tetramethyldiaminobenzene (1-Brmo-3,5-tetramethylaminobenzene, 1-Br-3,5- (Me ₂ N) ₂ C ₆ H ₃ ) Synthesis

1-Bromo-3,5-diaminobenzene (2.80 g, 15 mmol) was dissolved in acetonitrile and p -formaldehyde (1.80 g, 60 mmol) was added at 0 ° C. After stirring for 3 minutes at room temperature, sodium cyanoborohydride (3.00g total, 48 mmol) was divided into four portions over 40 minutes, and then further stirred for 25 minutes. Glacial acetic acid was added until the solution was neutralized, and stirring was continued for 45 minutes. Then, all solvents were removed and a 2 normal KOH aqueous solution was added until the pH was 9. The organic layer was extracted with ethyl acetate (3 × 50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The oil thus obtained was purified by column chromatography (silica gel, ethyl acetate / normal hexane = 1/9) to obtain 0.40 g of an off-white solid 1-bromo-3,5- ( N , N , N ', N'- tetra Methyldiaminobenzene was obtained in 11% yield.

¹ H NMR and ¹³ C { ¹ H} NMR confirming the synthesis of 1-bromo-3,5- ( N , N , N ', N'- tetramethyldiaminobenzene, and the results of mass spectrometry Indicated.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.26 (d, 2H), δ 5.88 (s, 1H), δ 2.90 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 152.3, 124.0, 104.9, 95.4, 40.6.

Synthesis Example 3-2

1- (3,5- N , N , N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene (1- (3,5-tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene, (3,5-Me ₂ NC ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

1-bromo-3,5- ( N , N , N ', N'- tetramethyldiaminobenzene (1.21) instead of 3-bromo- N , N -dimethylaniline used in Synthesis Example 2-1 g, 5 mmol) except that the reaction proceeds under the same conditions as in [Synthesis Example 2-1], and 0.53 g of pale yellow high chain 1- (3,5- N , N , N ', N' -tetramethyl-diamino-phenyl) -3,4-dimethyl-cyclopentadiene can be obtained in 41% yield.

The 1- (3,5- N, N, N ', N'- tetramethyl-diamino-phenyl) ¹ H confirming the synthesis of 3,4-dimethyl cyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.62 (s, 1H), δ 6.33 (d, 2H), δ 6.01 (s, 1H), δ 3.28 (s, 2H), δ 2.95 (d, 12H) , δ 1.97 (s, 3H), δ 1.90 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 151.8, 144.1, 137.5, 135.2, 131.1, 99.9, 96.9, 45.6, 41.0, 13.4, 12.6.

Synthesis Example 3-3

Bis [1- (3,5- N , N , N ', N'- Tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5-tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5 -(Me ₂ N) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1- (3,5- N , N , N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadiene (0.513 g, 2.0 mmol) synthesized in Synthesis Example 3-2 above Except for using tetrachlorobis (tetrahydrofuran) zirconium (0.377g, 1mmol), the reaction was carried out in the same manner as in [Synthesis Example 2-2] to give a bis- [1- ( 0.321 g (48% yield) of 3,5- N , N , N ', N' -tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride was obtained.

¹ H confirming the synthesis of the bis- [1- (3,5- N , N , N ', N'- tetramethyldiaminophenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.26 (s, 4H), δ 6.25 (d, 4H), δ 6.00 (s, 2H), δ 2.98 (s, 24H), δ 1.85 (s, 12H) .

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 152.1, 134.8, 127.7, 124.5, 116.9, 100.0, 96.6, 40.8, 13.4.

Anal. Calcd for C ₃₄ H ₄₆ Cl ₂ N ₄ Zr: C, 60.69; H, 6.89; N, 8.33.

Found: C, 60.45; H, 6. 80; N, 8.66.

Synthesis Example 4

Bis [1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 4-1 1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadiene, ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

40 ml of 4-methoxyphenylmagnesium bromide (20 mmol) was slowly added to a 3,4-dimethylsiglopenta-2-enone (2.20 g, 20 mmol) / 20 ml tetrahydrofuran solution at -78 ° C. The reaction solution was raised to room temperature and stirred overnight. A suitable amount of saturated aqueous ammonium chloride solution was added to the obtained orange solution to terminate the reaction. Then, the organic layer was extracted with diethyl ether (50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed on the rotary evaporator from the filtered solution to give an orange oil. The oil was dissolved in methylene chloride (30 mL), para-toluenesulfonic acid hydrate (ca. 0.1 g) was added thereto, and the mixture was stirred at room temperature for 1 hour. After appropriate removal of the solvent by rotary evaporator, recrystallization with ethanol at -20 ° C yielded 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene (2.20 g, 47% yield).

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.36 (d, 2H), 6.81 (d, 2H), 6.50 (s, 1H), 3.79 (s, 3H), 3.22 (s, 2H), 1.95 (s , 3H), 1.87 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 158.1, 142.2, 135.4, 134.7, 129.8, 129.6, 125.7, 113.9, 55.3, 45.3, 13.4, 12.6.

Synthesis Example 4-2

Bis [1- ( p -Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

1.202 g (6.0 mmol) of 1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene synthesized in [Synthesis Example 4-1] was carried out in the same manner as in [Synthesis Example 1-2]. Yellowish microcrystalline bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride 0.891 g (53% yield) was obtained.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.38 (d, 4H), 6.96 (d, 4H), 6.16 (s, 4H), 3.85 (s, 6H), 1.78 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.0, 127.7, 126.5, 126.1, 122.7, 115.4, 114.5, 55.4, 13.2. Anal. Calcd for C ₂₈ H ₃₀ Cl ₂ O ₂ Zr: C, 59.98; H, 5.39.

Found: C, 59.63; H, 5.64.

Synthesis Example 5

Bis [1- ( m -Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 5-1

One-( m -Methoxyphenyl) -3,4-dimethylcyclopentadiene (1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadiene, ( m -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

Dissolve 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) in 20 mL of tetrahydrofuran, and slowly add 1 equivalent of 3-methoxyphenylmagnesium bromide (20 mmol) at -78 ° C. gave. The reaction solution was raised to room temperature and stirred overnight. The reaction was terminated by adding an appropriate amount of saturated aqueous ammonium chloride solution to the solution. Then, the organic layer was extracted with diethyl ether (50 mL), collected, dried over anhydrous magnesium sulfate, and filtered. The filtered solution was removed by solvent in a rotary evaporator to obtain an oily intermediate. The oil was dissolved in methylene chloride (30 mL) again, and then paratoluenesulfonic acid hydrate (approximately 0.1 g) was added and stirred at room temperature for 1 hour. The solvent was removed using a rotary evaporator, and the oil thus obtained was purified by column chromatography (silica gel, ethyl acetate / normal hexane = 1/10) to obtain 1.00 g of pale yellow oil, 1- ( m -methoxyphenyl). -3,4-dimethylcyclopentadiene could be obtained in 25% yield.

The 1- (m - methoxyphenyl) ¹ H confirming the synthesis of 3,4-dimethyl cyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.18 (t, 1H), 7.03 (d, 1H), 6.96 (t, 1H), 6.69 (dd, 1H), 6.64 (s, 1H), 3.80 (s , 3H), 3.24 (s, 2H), 1.96 (s, 3H), 1.88 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.8, 142.3, 137.8, 136.1, 135.5, 132.1, 129.4, 117.3, 111.4, 110.2, 55.2, 45.3, 13.4, 12.6.

Synthesis Example 5-2

Bis [1- ( m -Methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( m -MeOC ₆ H ₄ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

[Synthesis example 2-2], except that 1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadiene (0.801 g, 4.0 mmol) synthesized in Synthesis Example 5-1 was used. The reaction was carried out in the same manner as in the] to obtain 0.519 g (46% yield) of bis- [1- ( m -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a light yellow solid.

The bis [1- (m - methoxyphenyl) -3,4-dimethyl-cyclopentadienyl] ¹ H confirming zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.35 (t, 2H), 7.05 (d, 2H), 6.98 (t, 2H), 6.82 (dd, 2H), 6.22 (s, 4H), 3.85 (s , 6H), 1.79 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 160.2, 134.8, 130.2, 128.3, 122.1, 117.6, 116.4, 113.0, 110.8, 55.3, 13.2.

Anal. Calcd for C ₂₈ H ₃₀ Cl ₂ O ₂ Zr: C, 59.98; H, 5.39.

Found: C, 60.59; H, 5.62.

[Synthesis Example 6]

Bis [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5- (MeO) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 6-1

1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene (1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene, (3,5- (MeO) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

1-bromo-3,5-dimethoxybenzene (4.34 g, 20 mmol) was dissolved in 20 mL of diethyl ether and then 1 equivalent of normal butyllithium (8.0 mL) was added at 0 ° C. After stirring at room temperature for 2 hours, the temperature was lowered to -78 ° C and 20 mL of tetrahydrofuran solution in which 1 equivalent of 3,4-dimethylcyclopenta-2-enone (2.20 g, 20 mmol) was added was added dropwise. Slowly put up and stir overnight. Next, the reaction was carried out in the same manner as in [Synthesis Example 5-1], and the obtained yellow oil was dissolved in ethanol and recrystallized at -20 ° C to give 1.31 g of pale off-white solid 1- (3,5). -Dimethoxyphenyl) -3,4-dimethylcyclopentadiene was obtained in 33% yield.

¹ H confirming the synthesis of 1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene NMR and ¹³ C { ¹ H} NMR results are shown below.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.64 (s, 1H), 6.59 (d, 2H), 6.28 (t, 1H), 3.79 (s, 6H), 3.23 (s, 2H), 1.96 (s , 3H), 1.88 (s, 3H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 160.9, 142.3, 138.3, 136.2, 135.4, 132.4, 102.8, 98.3, 55.3, 45.4, 13.4, 12.6.

Synthesis Example 6-2

 Bis [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- (3,5- (MeO) ₂ C ₆ H ₃ ) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

[Synthesis Example 2], except that 1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadiene (0.921 g, 4.0 mmol) synthesized in Synthesis Example 6-1 was used. 0.42 g (36% yield) of bis- [1- (3,5-dimethoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride as a yellow solid Got.

The bis [1- (3,5-dimethoxyphenyl) -3,4-dimethyl-cyclopentadienyl] ¹ H confirming zirconium dichloride The results of NMR and ¹³ C { ¹ H} NMR and their elemental analysis are as follows.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 6.59 (d, 4H), 6.39 (d, 2H), 6.19 (s, 4H), 3.83 (s, 12H), 1.85 (s, 12H).

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 161.4, 135.5, 128.3, 122.3, 116.7, 103.5, 99.4, 55.4, 13.3.

Anal. Calcd for C ₃₀ H ₃₄ Cl ₂ O ₄ Zr: C, 58.05; H, 5.52.

Found: C, 58.61; H, 5.66.

[Synthesis Example 7]

Bis- [1- ( p -Methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -OMePhPh) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

Synthesis Example 7-1

One-( p -Methoxybiphenyl) -3,4-dimethylcyclopentadiene (1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadiene, 1- ( p -OMePhPh) -3,4-Me ₂ C ₅ H ₃ ) Synthesis

4-bromo-4'-methoxybiphenyl (2.631 g, 10 mmol) was dissolved in 50 mL of diethyl ether and then 1 equivalent of n- BuLi (4.0 mL) was added at 0 ° C. After raising the temperature to room temperature and stirring for 2 hours, the solvent was evaporated, and the obtained lithium salt was dissolved in 20 mL of THF at -78 ° C, and then the same amount of 3,4-dimethylsiglopenta-2-enone ( 1.10 g, 10 mmol) was added dropwise through a cannula 20 mL solution was slowly raised to room temperature and stirred overnight. The reaction was terminated by adding an appropriate amount of saturated aqueous NH ₄ Cl solution to the yellow solution, and then extracted with diethyl ether (50 mL) to collect only the organic layer and dried over anhydrous magnesium sulfate and filtered. The solvent was removed from the rotary evaporator to obtain a yellow oil. The oil was dissolved in dichloromethane (30 mL), and then p- TsOH (ca. 0.1 g) was stirred for 1 hour at room temperature. Solid was formed. After evaporation of the solvent with a rotary evaporator, ethanol (30 mL) was poured into the obtained solid and filtered using Glass Frit. Washed with diethyl ether (10 mL), n- pentane (10 mL) and dried in vacuo afforded 1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadiene in 55% yield.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.52 (dd, 2H), 7.47 (s, 4H), 6.95 (dd, 2H), 6.68 (s, 1H), 3.83 (s, 3H), 3.29 (s , 2H), 1.98 (s, 3H), 1.90 ppm (s, 3H)

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.0, 142.1, 138.2, 135.9, 135.6, 134.8, 133.5, 131.6, 127.8, 126.7, 124.9, 114.2, 55.3, 45.2, 13.5, 12.6 ppm.

Synthesis Example 7-2

Bis- [1- ( p -Methoxybiphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride (Bis- [1- ( p -methoxyphenyl) -3,4-dimethylcyclopentadienyl] zirconium dichloride, [1- ( p -OMePhPh) -3,4-Me ₂ C ₅ H ₂ ] ₂ ZrCl ₂ ) Synthesis

0.829 g (3.0 mmol) of 1- ( p -methoxybiphenyl) -3,4-dimethylcyclopentadiene obtained in [Synthesis Example 7-1] was dissolved in 20 mL diethyl ether, followed by equivalents at -78 ° C. n- BuLi (1.2 mL) was added. After raising to room temperature and stirred for 4 hours. The solvent was evaporated and the white lithium salt obtained was mixed with half equivalent of ZrCl ₄ (thf) ₂ (1.5 mmol, 0.566 g) and dissolved in toluene (30 mL) at -78 ° C. The mixed solution was slowly warmed to room temperature and stirred while heating to 50 ° C. overnight. Then, LiCl was removed by Celite filtration and the solvent was evaporated. Then 0.642 g of bis- [1- ( p -methoxybiphenyl) -3,4 -Dimethylcyclopentadienyl] zirconium dichloride 60% yield was obtained. In addition, when recrystallized at -20 ℃ with dichloromethane / hexane solution to give a yellow crystalline solid.

¹ H NMR (400.13 MHz, CDCl ₃ ): δ 7.64 (d, 4H), 7.58 (d, 4H), 7.51 (d, 4H), 7.00 (d, 4H), 6.31 (s, 4H), 3.86 (s , 6H), 1.80 ppm (s, 12H)

¹³ C { ¹ H} NMR (100.62 MHz, CDCl ₃ ): δ 159.4, 139.6, 132.7, 131.6, 128.3, 127.9, 127.1, 125.6, 122.1, 116.0, 114.4, 55.4, 13.2 ppm

Anal. Calcd for C ₄₀ H ₃₈ Cl ₂ O ₂ Zr: C 67.39, H 5.37

Found: C 66.83, H 5.52.

[Example of Polymerization of Poly (1-butene) by Atmospheric Polymerization Method]

All polymerization proceeded with constant 1-butene pressure after injection of the required amount of solvent, catalyst, cocatalyst, 1-butene and the like in a reactor completely isolated from outside air. Solvents such as toluene used in the polymerization were purchased from Sigma-Alsrich, Anhydrous Grade, and then further dried by passing through an activated molecular sieve ( Molecular Sieve, 4A) or activated alumina layer. MAO (methylaluminoxane, Methylaluminoxane) was used as a 10% toluene solution of Albemarle (HS-MAO-10%) and then dried to a solid state. As a conventional metallocene catalyst having a complicated structure, a racemic-ethylene (bisindenyl) zirconium dichloride ( rac -Ethylene (bisIndenyl) zirconium dichloride, rac -C ₂ H ₄ (Ind) ₂ ZrCl ₂ ) catalyst is a Strem It was purchased from and used without further purification, bisdendenyl zirconium dichloride (Ind ₂ ZrCl ₂ ) was synthesized using the reference to the literature.

The molecular weight and molecular weight distribution of poly (1-butene) produced after polymerization were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method, and melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments) method.

[Polymerization Example 1]

In a 250 ml glass flask in which the inside was replaced with nitrogen in a glove box, 0.29 g of MAO (5 mmol) was added thereto, and toluene (48 ml) was added at room temperature, and then adjusted to 0 ° C. While stirring for 30 minutes, 1-butene gas was saturated to 1 bar. Next, toluene solution (2.0 ml, 5.0 mmol of Zr) in which the catalyst of [Synthesis Example 1-2] was dissolved was added to the polymerization by a syringe. After maintaining 1 bar and 0 ° C. for 2 hours, 5 ml of 10% HCl ethanol mixed solution was added to the polymerization solution to terminate the polymerization. Additional 200mL of ethanol was added to precipitate the polymer, stirred for about an hour and filtered. The filtered poly (1-butene) was dried for at least 15 hours while heating to 80 ° C. using a vacuum oven to finally obtain poly (1-butene).

[Polymerization Example 2]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 1], but polymerization was carried out at 25 ° C.

[Polymerization Example 3]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 1], but polymerization was carried out at 50 ° C.

 [Polymerization Example 4]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 1], but polymerization was carried out at 50 ° C. using the catalyst of Synthesis Example 4-2 instead of the catalyst of Synthesis Example 1-2.

[Polymerization Example 5]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 4], but polymerization was carried out at 70 ° C.

[Polymerization Comparative Example 1]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 1], but polymerization was performed at 50 ° C. using racemic-ethylene (bisindenyl) zirconium dichloride instead of the catalyst of [Synthesis Example 1-2].

[Polymerization Comparative Example 2]

1-butene polymerization was carried out in the same manner as in [Comparative Polymerization Example 1], but polymerization was performed using bisdenyl zirconium dichloride instead of racemic-ethylene (bisindenyl) zirconium dichloride.

[Polymerization of Poly (1-butene) by High Pressure Bulk Polymerization]

All polymerization proceeded with constant 1-butene pressure after injection of the required amount of solvent, catalyst, cocatalyst, 1-butene, etc. in a reactor (Autoclave) completely isolated from outside air. Solvents such as toluene used in the polymerization are purchased from Sigma-Aldrich, Anhydrous Grade, and then further dried by passing through an activated molecular sieve ( Molecular Sieve, 4A) or activated alumina layer. MAO (methylaluminoxane, Methylaluminoxane) was used as a 10% toluene solution of Albemarle (HS-MAO-10%) and then dried to a solid state.

The molecular weight and molecular weight distribution of the poly (1-butene) produced after polymerization were measured by GPC (Gel Permeation Chromatography, PL-GPC220) method, and melting point was measured by DSC (Differential Scanning Calorimetry, TA Instruments) method.

In this polymerization example, poly (1-butene) was produced by high pressure bulk polymerization for commercial production. Solvent is not used separately in this bulk polymerization, and monomer 1-Butene serves as a monomer and solvent. Therefore, this bulk polymerization method can simplify the separation process because no solvent is used separately.

[Polymerization Example 6]

The catalyst solution used for the polymerization was activated by dissolving 0.4 g of MAO (6.82 mmol based on Al) and 2 mg of the catalyst of [Synthesis Example 1-2] together in 25 ml toluene at room temperature.

The interior of a stainless steel autoclave with an internal volume of 100 ml was completely replaced with nitrogen. While maintaining the nitrogen purge (Purging), was added 2.2ml of the catalyst solution at room temperature and then added to 60ml of 1-butene, polymerization was performed for 1 hour at 30 ℃. After the completion of polymerization, the mixture was kept at room temperature, and excess 1-butene was removed through the discharge line to obtain a white powdery solid. The white solid powder thus obtained was dried for at least 15 hours while heating to 80 ° C. in a vacuum oven to finally obtain poly (1-butene).

[Polymerization Example 7]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 6], but polymerization was carried out at 50 ° C.

[Polymerization Example 8]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 6], but polymerization was carried out at 70 ° C.

[Polymerization Example 9]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 6], but polymerization was carried out at 90 ° C.

[Polymerization Example 10]

1-butene polymerization was carried out in the same manner as in [Polymerization Example 6], but polymerization was carried out at 110 ° C.

The results from [Polymerization Example 1] to [Polymerization Example 10] and the results of [Polymerization Comparative Example 1] and [Polymerization Comparative Example 2] are summarized in the following [Table 1], and each poly obtained as described above. Physical properties of the (1-butene) polymer are summarized in Table 2 below.

TABLE 1

Polymerization Example catalyst yield
(g) activation ^a One ^b 1-2 1.34 134 2  ^b 1-2 2.24 224 3  ^b 1-2 3.50 350 4  ^b 4-2 1.16 116 5  ^b 4-2 1.82 182 6 ^c 1-2 0.14 560 7  ^c 1-2 0.15 600 8  ^c 1-2 0.17 680 9  ^c 1-2 0.16 640 10  ^c 1-2 0.14 480 Comparative Example 1  ^d EBIZr ^e 16.7 10020 Comparative Example 2  ^b BIZr ^f 2.21 221 Unit: (kg of PP) / ((mol of Zr) r), ^b polymerization conditions: P (1-Butene), 1 bar; [Zr], 5.0 μmol; [Al] / [Zr], 1000; solvent, 50 mL of Toluene; t _p , 120 min. ^c polymerization conditions: [Zr], 0.3 µmol; [Al] / [Zr], 2000; 60 mL 1-Butene; t _p , 60 min., ^d Polymerization conditions: P (1-Butene), 1 bar; [Zr], 5.0 μmol; [Al] / [Zr], 1000; solvent, 50 mL of Toluene; t _p , 20 min., ^e rac- (C ₂ H ₄ ) (Ind) ₂ ZrCl ₂ , ^f Ind ₂ ZrCl ₂

TABLE 2

Polymerization Example Molecular Weight (M _w )
(× 10 ^-3 ) Molecular Weight Distribution (MwD, M _w / M _n ) Melting point
(° C) One 1,210 7.39 104.5 2 314 7.23 102.4 3 46 10.90 93.0 4 1,750 4.70 97.4 5 856 5.32 96.8 6 185 4.93 93.0 7 141 4.36 92.3 8 133 3.78 92.0 9 64 23.74 98.7 10 42 20.90 88.3 Comparative Example 1 16 2.22 73.9 Comparative Example 2 12 2.65 -

As shown in Tables 1 and 2, when the poly (1-butene) polymerization is carried out using the catalyst system of the present invention, as shown in Comparative Example 1, the interaction between the catalyst and the cocatalyst is eliminated without using a catalyst having a complicated structure. Through molecular weight and high melting point, it is possible to obtain crystalline poly (1-butene).

In addition, the molecular weight and molecular weight distribution of the poly (1-butene) can also be adjusted by appropriately adjusting the kind of hetero atoms in the catalyst and polymerization conditions. For example, in Polymerization Example 1 and Polymerization Example 4, the catalysts used were different, and thus the heteroatoms in the catalysts were different, resulting in poly (1-butenes) having different molecular weights and molecular weight distributions. I could confirm it.

This effect is caused by having heteroatoms in the catalyst which can interact with the promoter, which was confirmed by directly comparing the polymerization example with the polymerization comparative example.

As described above, the detailed description of the present invention has been made with reference to the accompanying drawings and embodiments. However, since the above-described embodiments have only been described with reference to preferred examples of the present invention, the present invention is limited to the above embodiments. It should not be understood that the scope of the present invention is to be understood by the claims and equivalent concepts described below.

Claims (11)

(A) a transition metal compound represented by the following [Formula I]; And Formula I

In [Formula I], M is selected from the group consisting of Group 3-10 elements on the periodic table, Cp ¹ and Cp ² are ligands each having a cyclopentadienyl skeleton, each having one or more substituents selected from the group consisting of [Formula II-1] and [Formula II-2],   [Formula II-1]

[Formula II-2]

In [Formula II-1] and [Formula II-2], Z is an element of group 15 or 16 of the periodic table, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, and a silylalkyl group having 1 to 20 carbon atoms C6-C20 aryl (Aryl), C7-C20 arylalkyl, C7-C20 Alkylaryl, C6-C20 Arylsilyl and C6 It is selected from the group consisting of 6-20 silylaryl groups, m is 1 or 2 depending on the type of Z, p is an integer in the range 1-5, Other substituents bonded to Cp ¹ and Cp ² in addition to the substituents represented by [Formula II-1] and [Formula II-2], and not bonded to ZRm of the [Formula II-1] and [Formula II-2] The other substituent bonded to the carbon atom in the unsubstituted phenyl ring is hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an alkylsilyl group having 1 to 20 carbon atoms , C1-C20 silylalkyl group, C1-C20 haloalkyl group, C6-C20 aryl group, C7-C20 arylalkyl group, C7-C20 It may be an alkylaryl group, an arylsilyl group having 6 to 20 carbon atoms, a silylyl group having 6 to 20 carbon atoms, or a halogen group, and these substituents may be bonded to each other by a ring. Can form a In [Formula I], X is an alkyl group having 1 to 20 carbon atoms, C3-C20 cycloalkyl group, C1-C20 alkylsilyl group, C1-C20 silylalkyl group, C6-C20 aryl group, C7-C20 20 arylalkyl groups, 7 to 20 carbon atoms, 6 to 20 carbon atoms, 6 to 20 carbon atoms, 6 to 20 carbon atoms, 1 to 20 carbon atoms Alkoxy group, C1-C20 Alkylsiloxy group, C6-C20 aryloxy group, Halogen group, Amine group and Tetrahydroborate group Selected from the group consisting of, n is an integer in the range of 1 to 5, depending on the central metal. (B) A catalyst for producing poly (1-butene) comprising a promoter compound selected from the group consisting of an aluminoxane compound represented by the following [Formula III-1] and an organoaluminum compound represented by the following [Formula III-2]. [Formula III-1]

In [Formula III-1], R ¹ is an alkyl group having 1 to 10 carbon atoms, and q is an integer within the range of 1 to 70. [Formula III-2]

In [Formula III-2], R ² , R ³ , R ⁴ are the same as or different from each other, and are each a C 1-10 alkyl group, a C 1-10 alkoxy group, or a halogen group, and R ² , R ³ And at least one of R ⁴ is an alkyl group having 1 to 10 carbon atoms. The method of claim 1, At least one substituent selected from the group consisting of the above [Formula II-1] and [Formula II-2] in the transition metal compound represented by the above [Formula I] is reacted with the cocatalyst compound (B) to form a poly ( A catalyst for producing poly (1-butene), characterized by adjusting the stereoregularity of 1-butene). The method of claim 1, M in [Formula I] is a catalyst for producing poly (1-butene), characterized in that the Group 4 elements on the periodic table. The method of claim 1, M in [Formula I] is a catalyst for producing poly (1-butene), characterized in that selected from zirconium (Zr), titanium (Ti) and hafnium (Hf). The method of claim 1, The ligand having the cyclopentadienyl skeleton in Cp ¹ and Cp ² of Formula [I] is selected from the group consisting of a cyclopentadienyl group, an indenyl group, and a fluorenyl group, wherein the poly (1-butene) Preparation catalyst. The method of claim 1, Z in [Formula II-1] and [Formula II-2] is nitrogen (Nitrogen, N), phosphorus (Phosphorus, P), arsenic (Arsenic, As), oxygen (Oxygen, O), sulfur (Sulfur, S ) And selenium (Selenium, Se) catalyst for producing poly (1-butene), characterized in that selected from the group consisting of. The method of claim 1, The aluminoxane compound represented by the above [Formula III-1] may be selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, butyl aluminoxane, hexyl aluminoxane, octyl aluminoxane and decyl aluminoxane. -Butene) catalyst for production. The method of claim 1, The organoaluminum compound represented by the above [Formula III-2] is selected from the group consisting of trialkylaluminum, dialkylaluminum alkoxide, dialkylaluminum halide, alkylaluminum dialkoxide and alkylaluminum dihalide. -Butene) catalyst for production. In the presence of the catalyst for poly (1-butene) polymerization of any one of Claims 1-8, 1-butene is superposed | polymerized or 1-butene is copolymerized with the compound containing a double bond, It is characterized by the above-mentioned. Method for producing poly (1-butene) Poly (1-butene) manufactured by the manufacturing method of Claim 9. The method of claim 10, Poly (1-butene), characterized in that the molecular weight distribution (M _w / M _n ) is 3 to 30.