KR100497170B1 - Metallocene catalyst and preparation method thereof - Google Patents

Abstract

The present invention relates to a metallocene catalyst and a method for preparing an olefin copolymer using the same, and in particular, a cyclopentadienyl group and a newly introduced cyclone derived from a pullbene compound having a substituent at the 2,5 position as an intermediate derivative. Metallocene catalysts having a substituent only at the alpha position of the bridge position carbon in the cyclopentadienyl group introduced from the fulbene derivative, and the pentadienyl group is bridged by one carbon, and an olefin air using the same It relates to a method for producing the coalescence.

The metallocene catalyst prepared by the present invention is a cyclic olefin copolymer (COC) because it is less steric hindrance and at the same time can provide a high electronic effect than the metallocene catalyst prepared using a fulvene compound obtained by a conventional method. It can be advantageously used for copolymerization of a monomer having a large size such as.

Description

Metallocene catalyst and preparation method thereof {METALLOCENE CATALYST AND PREPARATION METHOD THEREOF}

The present invention relates to a new metallocene catalyst and a method for preparing an olefin copolymer using the same, and more particularly, to prepare an organic fulvene compound for making a metallocene catalyst and to use the anion including a cyclopentadienyl group. The present invention relates to a metallocene catalyst having a substituent only at the alpha position of a cyclopentadienyl group through a reaction with a group, and a method for preparing an olefin copolymer using the same.

Group 4 transition metal compounds having one or two cyclopentadienyl groups as ligands can be used as a catalyst for olefin polymerization by activating with methylaluminoxane or boron compounds (US Pat. No. 5,580,939; Macromol. Chem. Phys. vol. 197, 1996 3707-3945). This catalyst exhibits unique characteristics that conventional Ziegler-Natta catalysts cannot achieve. In other words, the molecular weight distribution is narrow and the reactivity to the second monomers such as alpha olefins and cyclic olefins is good, and the polymer produced is also uniform in the second monomer distribution. Also, by changing the substituent of the cyclopentadienyl ligand, the stereoselectivity of the polymer can be controlled during the polymerization of alpha olefins (Angew. Chem. Int. Ed. Engl. 1995, 34, 1143), and when copolymerizing ethylene with other olefins The degree of copolymerization, molecular weight, second monomer distribution and the like can be adjusted (US Pat. No. 5,470,811).

With the development of this catalyst system, LLDPE, VLDPE, EPM, EPDM, which are copolymers of ethylene and alpha olefins, and cyclic olefin copolymers (COC), ethylene and alpha, which are copolymers of ethylene and cyclic olefins or alpha and cyclic olefins Efforts have been made to find suitable catalysts for the production of copolymers of olefins and styrene. Commonly required catalyst conditions for the preparation of these products are that they must be capable of producing polymers with good activity, good reactivity to the second monomer and a uniform distribution of the second monomer.

On the other hand, metallocene catalysts are more expensive than conventional Ziegler-Natta catalysts, and therefore have good activity and are economically valuable. If the reactivity with the second monomer is good, there is an advantage that a polymer containing a large amount of the second monomer can be obtained even with the addition of a small amount of the second monomer.

Several researchers have studied various catalysts and found that bridged catalysts generally have good reactivity with the second monomer. Specifically, FJ Karol's research indicates that in order to produce an LLDPE product with a density of 0.93 using hexene as the second monomer, the ratio of ethylene and hexene in the bridged catalyst should be only 0.004 to 0.005, but not bridged. For catalysts, the ratio is required up to 0.02 (April 18, 1997, Palm Coast, FL, Polymer Reaction Engineering Foundation Conference).

Therefore, attention is focused on bridged catalysts to produce the abovementioned copolymers. Bridged catalysts have also been studied for their ability to control the molecular structure of propylene polymers according to their symmetry.

The bridged catalysts studied so far can be classified into three types depending on the type of bridge. Obtained by reaction of an electrophile such as an alkyl halide with two cyclopentadienyl ligands by a reaction of indene or fluorene, a silicon bridged catalyst linked by -SiR _2- , a reaction of fulven with indene or fluorene Methylene bridged catalysts. Representative synthesis methods for these catalysts are shown in Schemes 1 to 3, respectively.

Scheme 1

Scheme 2

Scheme 3

In the above schemes, various substituents can be put in the cyclopentadienyl ring of the bridged catalyst starting from the absence of any substituents. However, when the ligand is synthesized by the conventional method, it is impossible to put the substituent only at the alpha position relative to the bridge position in the cyclopentadienyl group. The reason for this is that a method of synthesizing a ligand of a metallocene catalyst having only one carbon at the bridge position can be obtained by reacting fulven with an anion of a cyclopentadienyl derivative such as fluorene or indene (J. Amer. Chem). Soc., 110 (1988), 6255), because the process of making the fulbene is synthesized by reacting a cyclopentadienyl anion bearing a substituent with a carbonyl group. At this time, because of the steric hindrance effect, the substituents go to the beta position relative to the bridge position in the cyclopentadienyl group. Attacking a cyclopentadienyl anion with two substituents at positions 1 and 3 produces fulvenes with substituents at the alpha and beta positions, but no fulbenes with substituents at the alpha position.

On the other hand, there are two major influences on the activity of the metallocene catalyst and the steric structure of the polymer. First, the steric hindrance effect of the catalyst is a problem of how freely the monomer can enter the catalyst. The other is how electrons can stabilize the activated state of the catalyst, and when an electron-substituting substituent such as an alkyl group is substituted on the cyclopentadienyl ring, it can stabilize the activated state of the metallocene catalyst. It is advantageous for polymerization.

There are various kinds of metallocene catalysts prepared by using general fulven compounds as intermediates. One of them is a metallocene derivative having a cyclopentadienyl group and a fluorenyl group. The catalyst having the smallest steric hindrance is a catalyst without a substituent in the cyclopentadienyl group (US Pat. No. 5,087,677). Such catalysts are generally well known as catalysts for the production of cyclic olefin copolymers (COC), which are copolymers of ethylene with a larger monomer such as norbornene.

However, the metallocene catalyst prepared by the above method has been a subject of continuous study because there is much room for improvement in copolymerization activity even if the steric hindrance is small.

It is an object of the present invention to provide a metallocene catalyst having a low steric hindrance and excellent copolymerizability and polymerization activity and a method for producing the same, in consideration of the problems in the prior art as described above.

Another object of the present invention is to provide a method for producing a cyclic olefin copolymer (COC) using the metallocene catalyst.

In order to achieve the above object, the present invention provides a compound represented by the following formula (5).

[Formula 5]

In the formula (5),

R ₁ , R ₂ , R ₃ and R ₄ are each independently or simultaneously hydrogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Alkyl or aryl having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₃ and R ₄ may be linked to one another in a ring by an alkylidine radical comprising an alkyl or aryl radical;

A is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Indenyl or derivatives thereof; Substituted or unsubstituted amido groups; Or a substituted or unsubstituted phosphino group.

In the compound of Formula 5, R ₁ and R ₂ are methyl, one or both of R ₃ and R ₄ is phenyl, and A is preferably fluorenyl or a derivative thereof.

In addition, the present invention provides a metallocene catalyst represented by the following formula (1).

[Formula 1]

In the formula of Formula 1,

R ₁ , R ₂ , R ₃ and R ₄ are each independently or simultaneously hydrogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Alkyl or aryl having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₃ and R ₄ may be linked to one another in a ring by an alkylidine radical comprising an alkyl or aryl radical;

M is a Group 4 transition metal;

A is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Indenyl or derivatives thereof; Substituted or unsubstituted amido groups; Or a substituted or unsubstituted phosphino group; And

Q ₁ and Q ₂ are each independently or simultaneously halogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Substituted or unsubstituted alkylidene having 1 to 20 carbon atoms; Substituted or unsubstituted amido groups; Alkylalkoxy having 1 to 20 carbon atoms; Or an aryl alkoxy group.

In addition, the present invention

a) preparing a compound represented by the following Chemical Formula 5 by reacting a fulvene compound represented by the following Chemical Formula 7 with a cyclopentadiene derivative; And

b) providing a method for preparing a metallocene catalyst according to the above, comprising the step of reacting the compound represented by Formula 5 with the compound represented by Formula 6 to prepare a compound represented by Formula 1.

[Formula 5]

[Formula 6]

M (Q ₁ ) (Q ₂ )

[Formula 7]

In Formula 5, Formula 6 and Formula 7,

R ₁ , R ₂ , R ₃ and R ₄ are each independently or simultaneously hydrogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Alkyl or aryl having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₃ and R ₄ may be linked to one another in a ring by an alkylidine radical comprising an alkyl or aryl radical;

M is a Group 4 transition metal;

A is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Indenyl or derivatives thereof; Substituted or unsubstituted amido groups; Or a substituted or unsubstituted phosphino group; And

Q ₁ and Q ₂ are each independently or simultaneously halogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Substituted or unsubstituted alkylidene having 1 to 20 carbon atoms; Substituted or unsubstituted amido groups; Alkylalkoxy having 1 to 20 carbon atoms; Or an aryl alkoxy group.

In addition, the present invention is a method for producing an ethylene-based polyolefin copolymer,

A polyolefin comprising the step of polymerizing at least one monomer selected from the group consisting of ethylene, α-olefins, diene monomers, triene monomers, and styrene monomers under a metallocene catalyst of formula (1) according to claim 3 It provides a method for producing a copolymer.

In addition, the present invention is a method for producing a cyclic olefin copolymer (COC),

It provides a method for producing a cyclic olefin copolymer comprising the step of polymerizing α-olefin and cyclic olefin under a metallocene catalyst represented by the formula (1).

Hereinafter, the present invention will be described in detail.

The present invention avoids the synthesis of fulbene through the synthesis of cyclopentadienyl anion or cyclopentadiene and an electrophile, and uses alpha bromoketone having a substituent at the beta position as a starting material at the desired 2,5 position. An organic fulvene derivative having a substituent was prepared, using this as an intermediate, and there was only one carbon at the bridge position of the bridged metallocene catalyst, and only at the alpha position relative to the bridge position carbon of the cyclopentadienyl ligand derived from fulvene. It is to prepare a metallocene catalyst having a substituent. The present invention also provides a method for preparing a cyclic olefin copolymer using the metallocene catalyst thus prepared.

Metallocene catalysts having substituents only at the alpha position of the cyclopentadienyl group of the present invention have advantages in many respects. That is, in the method for preparing the cyclic olefin copolymer, the portion where monomers enter and the polymer grows is opposite to the bridge, i.e., beta position relative to the bridge position in the cyclopentadienyl group. However, since the metallocene catalyst of the present invention has a substituent only in the alpha position, the steric hindrance of the substituent is reduced and the electronic effect of the catalyst is achieved so that the activity of the polymerization reaction can be increased. Therefore, since the metallocene catalyst of the present invention does not have a substituent at the beta position, it is easy to accept a monomer having a large steric hindrance when reacting, thereby facilitating copolymerization.

In the metallocene catalyst of Chemical Formula 1 of the present invention, it is preferable that A is fluorenyl or a derivative thereof, and that R ₁ , R ₂ , R ₃ and R ₄ are simultaneously alkyl or aryl radicals having 1 to 20 carbon atoms. . In addition, the metallocene catalyst of Formula 1 is preferably R ₁ and R ₂ is methyl and R ₃ and R ₄ is one or both of them phenyl. In addition, the metallocene catalyst of Formula 1 is A is indenyl or a derivative thereof, it is preferable that R ₁ , R ₂ , R ₃ and R ₄ are alkyl or aryl having 1 to 20 carbon atoms at the same time. In addition, the metallocene catalyst of the general formula (1) is a substituted or unsubstituted amido group, it is preferable that R ₁ , R ₂ , R ₃ and R ₄ are alkyl or aryl having 1 to 20 carbon atoms at the same time. In addition, the metallocene catalyst of Chemical Formula 1 is a substituted or unsubstituted phosphino group, and R ₁ , R ₂ , R ₃ and R ₄ are metallocene catalysts having 1 to 20 carbon atoms or alkyl at the same time. It is preferable.

The method for preparing the metallocene catalyst of the present invention follows the following Scheme 4.

Scheme 4

The present invention is described in the literature using alphabromo unsaturated ketone of formula 14 having substituent R ₂ at beta position which is commercially available from a reagent company such as Aldrich, as shown in Scheme 4. By converting the carbonyl group by the conventional method, a compound of formula 13, which is a dioxolane group derivative, may be obtained (J. Amer. Chem. Soc. 1988, 110,4741).

Thereafter, the compound of Formula 13 may be made into a lithium salt using butyllithium or the like under an atmosphere of removing water at low temperature (preferably, −78 ° C.), and then reacted with an electrophile of Formula 12 to obtain a compound of Formula 11 . In this case, the form of R ₃ and R ₄ may be determined by the structure of the electrophile. The ketal group protecting the carbonyl (dioxolane group) can be easily decomposed by column chromatography, which is a purification process of the reactant, and can be easily obtained by hydrolysis by acid treatment even without a column.

Next, a method of preparing the compound of Formula 9 from the compound of Formula 11 may be prepared by making a protecting group of alcohol (Protective groups in Organic synthesis, 3 ^rd Ed. (TW Green 1999)). That is, the present invention reacts with the protection of alcohol by reacting a compound of Formula 11 with a compound of Formula 10 or a compound having a double bond such as dihydropyran or isobutene and used for protecting the alcohol. The compound of can be prepared. In Chemical Formula 9, a protective group R ₅ may be used in various ways. Preferably, the compound reacted with Formula 11 is preferably obtained through the use of dihydropyrane, which is a well-known protecting group, or by reaction of an anion with an alkyl halide of the compound of Formula 10. If there are associations, various protection groups can be used.

Next, in order to prepare a fulvene compound of the formula (7) from the compound of the formula (9), a trivalent alcohol can be obtained by nucleophilic attack of the organometallic compound of the formula (8a) or (8b) to the ketone compound of the formula (3), When the alcohol is dehydrated by acid treatment, cyclopentadiene containing the protecting group R ₅ of alcohol is obtained.

[Formula 8a]

R ₁ -M

[Formula 8b]

R ₁ -MgX

In the formula of Formula 8a and Formula 8b,

R ₁ is hydrogen; Alkyl having 1 to 20 carbon atoms with or without an oxygen atom or a nitrogen atom, or aryl; Alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl;

X is a halogen atom;

M is an alkali metal comprising Li or Na.

At this time, it is possible to adjust the R ₁ group of the fulvene compound obtained according to the type of organometallic compound to react. That is, the organometallic compound represented by Chemical Formula 8a may use alkyl lithium having 1 to 20 carbon atoms, or aryl lithium, or may use a Grignard reagent of Chemical Formula 8b.

Then, when the cyclopentadiene is dehydrogenated to a strong base such as sodium ethoxide to form a cyclopentadienyl anion, a protective group such as THP may fall off to obtain a desired fulven compound.

Then, in the present invention, when the cyclopentadiene dehydrogenated to a strong base such as sodium ethoxide to form a cyclopentadienyl anion, an oxygen atom and a protecting group such as tetrahydropyranyl (THP) group become anions and fall off. The desired fulvene compound can be obtained.

Then, the present invention can be easily obtained by reacting the fulvene compound of formula 7 having a substituent at the 2,5 position with an anion of the cyclopentadiene derivative. The cyclopentadiene derivatives to be reacted include cyclopentadienyl or derivatives thereof, fluorenyl or derivatives thereof, indenyl or derivatives thereof, substituted or unsubstituted amido groups, substituted or unsubstituted phosphino groups, and the like. Can be used.

Finally, the method for preparing the metallocene catalyst of the compound of the formula (1) in the compound of the formula (5) is possible by a variety of methods reported in the literature, preferably prepared by reacting the compound of the formula Can be. Typically, two equivalents of normal-butyllithium are treated to dehydrogenate cyclopentadiene and fluorene groups to form cyclopentadienyl anions and fluorenyl anions, respectively, which can be obtained by reaction with metal halide compounds and the like. .

In this way, a metallocene catalyst containing a cyclopentadienyl group having only one carbon in the bridge position and having a substituent only at the alpha position obtained from fulven can be prepared.

In addition, the present invention may provide a cyclic olefin copolymer (COC) by polymerizing α-olefin and cyclic olefin using the metallocene compound of Formula 1 as a catalyst.

The present invention is a linear, circular or mesh compound represented by the formula (2); A compound represented by Formula 3; And at least one compound selected from the group consisting of a compound represented by the formula (4a) or a compound represented by the formula (4b) can be used as cyclic olefin copolymerization.

[Formula 2]

_{- [Al (R 6) -O} ] a -

In the formula (2),

Each R ₆ is independently or simultaneously halogen, a hydrocarbyl radical of 1 to 20 carbon atoms, or a hydrocarbyl radical of 1 to 20 carbon atoms substituted with halogen, and

a is an integer from 2 to 5000,

[Formula 3]

N (R ₆ ) ₃

In the formula (3),

N is aluminum,

Each of R ₆ independently or simultaneously is a halogen, a hydrocarbyl radical of 1 to 20 carbon atoms, or a hydrocarbyl radical of 1 to 20 carbon atoms substituted with halogen,

[Formula 4a]

[LH] ⁺ [NE ₄ ] ^-

[Formula 4b]

[L] ⁺ [NE ₄ ] ^-

In Formulas 4a and 4b,

L is a neutral or cationic Lewis acid,

H is a hydrogen atom,

N is a Group 13 element on the periodic table,

Each of four E's independently or simultaneously is an aryl radical having 6 to 20 carbon atoms substituted with at least one substituent selected from the group consisting of halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, and phenoxy radicals .

Examples of the compound represented by Formula 2 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like.

Examples of the alkyl metal compound of Formula 3 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl Boron, triisobutyl boron, tripropyl boron, tributyl boron and the like.

Examples of the compounds of Formulas 4-a and 4-b include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-tripololomethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tri Butyl ammonium tetrapentafluorophenyl boron, N, N-diethyl amyldium tetratetyl boron, N, N-diethylanilidedium tetraphenyl boron, N, N-diethylanilinium tetrapentafluorophenyl Boron, diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, tri Tyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (p-tolyl) aluminum, tripropyl ammonium tetra (p-tolyl) aluminum, triethyl ammonium tetra (o, p-dimethylphenyl Aluminum, tributyl ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethyl ammonium tetra (p-trifluoromethylphenyl) aluminum, tributyl ammonium tetrapentafluorophenylaluminum, N, N-diethyl anyl Linium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium Tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, trimethylammonium Triphenylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl) boron, Trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentaflo Rophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium Tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarbonium tetra (p-tripulomethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, and the like.

The metallocene catalyst and the cocatalyst of the formula (1) may be used in a form supported on silica or alumina.

Examples of the olefin monomer that can be polymerized using the catalyst and the promoter include ethylene, alpha olefin, cyclic olefin, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds can also be polymerized. . Examples of such monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-decene, 1-undecene, 1-dodecene, 1-tetra Decene, 1-hexadecene, 1-atocene, norbornene, norbornadiene, ethylidenenorbornene, phenyl norbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers can be mixed and copolymerized 2 or more types.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these Examples are only for illustrating the present invention and the present invention is not limited to these.

EXAMPLE

Organic reagents and solvents necessary for the preparation of the catalyst were purchased from Aldrich and Merck, and used by purification in a standard manner. The reproducibility of the experiment was improved by blocking contact between air and moisture at all stages of the catalyst synthesis. To demonstrate the structure of the catalyst, the spectrum was obtained by dissolving in CDCl ₃ solvent using 300 MHz Bruker nuclear magnetic resonance (NMR).

Example 1

(Catalyst production)

(Synthesis of Benzylidene (Fluorenyl) (1,3-dimethylcyclopentadienyl) zirconium dichloride (Compound of Formula 1))

1) Ketal substituent of 2-bromo-3-methyl-cyclophen-2-enone (Compound 10)

Carbonyl group by the method described in J. Amer. Chem. Soc. 1988, 110, 4741, starting with 2-bromo-3-methyl-cyclophen-2-enone purchased from Aldrich. Was converted to prepare a ketal (dioxolane group) derivative 10.

2) 2- (Hydroxy-phenyl-methyl) 3-methyl-cyclophen-2-enone (Compound 9)

After dissolving 0.550 g (2.54 mmol) of Compound 10 in 9.0 mL of tetrahydrofuran, 1.02 mL (2.54 mmol) of normal-butyllithium at 2.5 mol concentration was added dropwise at -78 ° C to react slowly for 1 hour to form a lithium salt. . 0.270 g (2.54 mmol) of benzaldehyde was slowly added to the reaction mixture, and the reaction was continued at the same temperature for about 1 hour. The reaction mixture was poured into a separatory funnel containing 10 mL of distilled water, extracted with 30 ml of ethyl acetate, the residual moisture was removed with magnesium sulfate, and the solvent was removed by vacuum distillation. The product containing the obtained impurity was separated by column chromatography using a mixture (v / v) of ethyl acetate and normal hexane 3: 1. The obtained dioxolane group is easily converted into a ketone compound during separation by silica gel during column chromatography. The yield of the obtained compound was 0.440 g (96%).

¹ H NMR (CDCl ₃ ): δ 7.20-7.36 (m, 5H), 5.59 (d, J = 9.1 Hz, 1 H, OH), 4.58 (d, J = 9.1 Hz, 1H, CH-O), 2.60-2.50 (m, 2H), 2.45 -2.35 (m, 2H), 2.10 (s, 3H, CH ₃ ) ppm. ¹³ C NMR (CDCl ₃ ): δ 210.60 (carbonyl), 172.18, 142.85, 140.04, 128.48, 127.44, 125.73, 70.14 (C-OH), 34.58, 32.07, 17.49 ppm.

3) 3-Methyl-2- [phenyl- (tetrahydropyran-2-yloxo) -methyl] -cyclophen-2-enone (Compound 8)

0.440 g (2.17 mmol) of compound 9 was dissolved in 9.0 mL of methylene chloride, 0.456 g (5.43 mmol) of dihydropyran was added at 20 ° C., and 4.13 mg (0.0217 mmol) of paratoluenesulfonic acid containing one water molecule per molecule was added. Put and stirred for 2 hours. 30 ml of ethyl acetate was added to the obtained reaction mixture, diluted with it, and washed twice with 5 mL of saturated sodium bicarbonate solution. After separation using a separatory funnel, the organic layer was taken, residual water was removed with magnesium sulfate, and the solvent was removed with a vacuum distillation. The product containing the obtained impurity was separated by column chromatography using a mixture (v / v) of ethyl acetate and normal hexane 3: 1. The yield of the obtained compound was 0.530 g (85%) proceeded to the next step without any further confirmation of the compound.

4) 2,5-dimethyl-6-phenylpulbene (Compound 7)

0.530 g (1.85 mmol) of Compound 8 was dissolved in 10.0 mL of diethyl ether, and 1.48 mL (2.22 mmol) of methyllithium at a molar concentration of 1.5 mol was added dropwise to a Schlenk flask at -78 ° C. After the reaction was raised to room temperature for 7 hours. 10 ml of distilled water was added to the obtained reaction mixture, and diethyl ether was removed by distillation under reduced pressure. 20 ml of ethyl acetate was added to the mixed solution from which diethyl ether was removed, and then the organic layer was taken with a separatory funnel, 20 ml of hydrochloric acid with 2 normal concentrations was added, and vigorously shaken for 3 minutes. The aqueous layer was taken out, the organic layer was taken, 20 mL of sodium hydrogen carbonate was added, the aqueous layer was taken out again, the organic layer was taken out, residual moisture was removed with magnesium sulfate, and the solvent was completely removed by vacuum distillation. The product containing the obtained impurity was dissolved in 5 ml of tetrahydrofuran, 46 mg (2.0 mmol) of NaH was added thereto, and 0.5 ml of methanol was added thereto. After reacting at room temperature for 3 hours to confirm the appearance of red color, the reaction mixture was dropped into a separatory funnel containing 40 ml of water and normal hexane, each of which was shaken, and only the organic layer was obtained. The solvent was removed with a distiller. The product containing the obtained impurity was separated by column chromatography using a mixture (v / v) of ethyl acetate and normal hexane 10: 1. The yield of the obtained compound was 0.200 g (63%).

¹ H NMR (CDCl ₃ ): δ 7.37-7.33 (m, 5H, ph-H), 7.29 (s, 1H, ph-CH), 6.08 (dq, J = 3.3, 1.7 Hz, 1 H, CH ₃ -C = CH), 6.01 (dq, J = 3.3, 1.7 Hz, 1H, CH ₃ -C = CH), 2.10 (s, 3H, CH ₃ ), 1.71 (s, 3H, CH ₃ ) ppm. ¹³ C NMR (CDCl ₃ ): δ 146.33, 136.67, 134.55, 133.52, 132.05, 130.01, 129.32, 129.03, 127.86, 126.97, 16.55 (CH ₃ ), 12.66 (CH ₃ ) ppm.

5) 2- [alpha-florenylbenzyl] -1,3-dimethylcyclopentadiene (Compound 5)

After dissolving 0.097 g (0.600 mmol) of fluorene in 3.0 mL of tetrahydrofuran, 0.24 ml (2.5 M in hexane, 0.600 mmol) of normal butyllithium was added dropwise at -30 ° C, and reacted for 1 hour. The compound 7 obtained above was added at 0.110 g (0.600 mmol) -30 ° C, and the solution was reacted at room temperature for about 2 hours. 4 mL of saturated aqueous ammonium chloride solution was added to a separatory funnel, and the reaction solution was poured, and an organic layer was taken with diethyl ether. The obtained organic layer was removed residual water with ammonium sulfate, the solvent was removed with a vacuum distillation, and the product containing impurities was separated by column chromatography using a mixture (v / v) of normal hexane and toluene 10: 1. The yield of the obtained compound was 0.160 g (76%).

¹ H NMR (C ₆ D ₆ ): δ 7.65 (d, J = 7.4 Hz, 2 H), 7.4-7.0 (m, 9 H), 6.94-6.89 (m, 2H), 5.81 (sextet, 1 H , J = 1.8 Hz, vinyl-H), 4.83 (d, J = 11.2 Hz, 1 H, Ph-CH or Ph-CHCH), 3.91 (d, J = 11.2 Hz, 1 H, Ph-CH or Ph- CHCH), 2.60 (quintet, J = 1.8 Hz, 2H, CH ₂ ), 1.86 (q, J = 1.8 Hz, 3H, CH ₃ ), 1.63 (s, 3H) ppm. ¹³ C NMR (C ₆ D ₆ ): δ 147.22, 146.67, 144.49, 143.38, 142.41, 141.60, 138.97, 137.88, 129.98, 129.33, 127.47, 126.86, 126.73, 126.66, 126.62, 126.44, 125.76, 119.83, 119.83. , 40.79, 44.42, 16.73, 14.92 ppm.

6) benzylidene (fluorenyl) (1,3-dimethylcyclopentadienyl) zirconium dichloride (compound 1)

0.108 g (0.310 mmol) of Compound 5 was dissolved in 3.0 mL of tetrahydrofuran, and 0.25 ml (2.5 M in hexane, 0.620 mmol) of normal butyllithium was added dropwise at -30 ° C, followed by stirring overnight. The obtained mixed solution was removed with a vacuum pump and then washed with 4.0 ml of normal pentane and 4.0 ml of benzene. 0.072 mg (0.31 mmol) of zirconium tetrachloride of compound 6 was reacted with red lithium salt obtained above under 8.0 ml of normal pentane solvent for 12 hours. The mixed solution obtained after the reaction was decanted and extracted with benzene to obtain a desired metallocene catalyst at 12 g (yield 76%).

¹ H NMR (CD ₂ Cl ₂ ): δ 8.1-6.9 (m, 13H), 6.80 (s, 1H), 6.28-6.19 (dd, 2H), 2.21 (s, 3H), 1.82 (s, 3H) ppm. ¹³ C-NMR (CD ₂ Cl ₂ ): δ 137.67, 128.43, 127.96, 127.75, 127.56, 127.10, 126.45, 126.28, 126.20, 124.94, 124.65, 124.41, 124.24, 124.19, 123.52, 123.41, 123.19. 121.22, 98.82, 73.59, 41.25, 18.80, 16.34 ppm.

Comparative Example 1

A commercially available isopropylene (9-fluorenyl) -cyclopentadienyl zirconium dichloride (product of Boulder) was used.

Example 2

(Polymerization of ethylene)

200 ml of toluene solution was placed in a pressure reactor. 1.8 ml of methylaluminoxane (6.9 wt% Al of toluene solution, density = 0.88c / ml, manufactured by Akzo) was added thereto. The reactor was immersed in a 70 ° C. thermostat and allowed to stand for 30 minutes to make the reactor temperature the same as the thermostat. 2 ml of the preparation catalyst a (1 μM concentration, toluene solution) was added to the reactor, and then rapidly stirred at 200 r.p.m while adding ethylene pressure at 60 psig. After 20 minutes, the obtained white solid compound was filtered to remove the solvent, acetone was added thereto, stirred at room temperature overnight, and then filtered to obtain a white solid polymer. It was vacuum dried to give 8.5 g of a polymer.

Example 3

(Copolymerization of Ethylene and Norbornene, a Type of Cyclic Olefin)

Norbornene was dissolved in toluene to make a 56 wt% solution and 200 ml was placed in a pressure reactor. 1.8 ml of methylaluminoxane (6.9 wt% Al of toluene solution, density = 0.88c / ml, manufactured by Akzo) was added thereto. The reactor was immersed in a 70 ° C. thermostat and allowed to stand for 30 minutes to make the reactor temperature the same as the thermostat. After adding 2 ml of the compound 1 (1 μM concentration, toluene solution) which is the metallocene catalyst prepared in Example 1 to the reactor, the mixture was rapidly stirred at 200 r.p.m while adding the ethylene pressure prepared in Example 2 to 60 psig. After 20 minutes the contents were poured into acetone solution to separate the white solid compound. The solvent was removed by filtration, acetone was added thereto, stirred at room temperature overnight, and then filtered to obtain a white solid polymer. This was dried under reduced pressure in vacuo to give 23.0 g of copolymer. Tg was checked at 170 ° C. using DSC.

Example 4

Experiments were carried out under the same methods and conditions as in Example 3, except that only the pressure conditions were changed to 30 psi. 8.5 g of copolymer were obtained and Tg was checked at 182 ° C. using DSC.

Example 5

Experiments were carried out under the same methods and conditions as in Example 3 except for changing the pressure conditions to 100 psi. 32.9 g of copolymer were obtained and Tg was confirmed at 149 ° C. using DSC.

Example 6

The polymerization was carried out in the same manner and in the same manner as in Example 3 except that the amount of the catalyst was increased to 4 ml. 41.2 g of copolymer were obtained and Tg was checked at 174 ° C. using DSC.

Example 7

The polymerization was carried out in the same manner and in the same manner as in Example 3 except that the reaction temperature was 30 ° C. 11.5 g of copolymer were obtained and Tg was checked at 157 ° C. using DSC.

Example 8

The polymerization was carried out in the same manner as in Example 3, except that the norbornene solution was 80% solution. 34.5 g of copolymer were obtained and Tg was checked at 202 ° C. using DSC.

Example 9

The polymerization was carried out in the same manner and in the same manner as in Example 3, except that the norbornene solution was 30% solution. 16.5 g of copolymer were obtained and Tg was checked at 162 ° C. using DSC.

Comparative Example 2

The polymerization was carried out in the same manner and in the same manner as in Example 3, using an isopropylene (9-fluoroenyl) -cyclopentadienyl zirconium dichloride catalyst commercially available from Boulder. Polymerized. 12.8 g of copolymer were obtained and Tg was checked at 170 ° C. using DSC.

Comparative Example 3

It carried out by the same method and conditions as the comparative example 2, and superposed | polymerized under 30 psi under the same catalyst. 6.9 g of copolymer were obtained and Tg was checked at 177 ° C. using DSC.

Comparative Example 4

It carried out by the same method and conditions as the comparative example 2, and superposed | polymerized by extending the quantity of catalyst to 4 ml under the same catalyst. 22.4 g of copolymer were obtained and Tg was checked at 173 ° C. using DSC.

As can be seen from the above results, Example 1 of the present invention is an alpha having a substituent at the beta position by avoiding a method of synthesizing fulbene through the synthesis of cyclopentadienyl anion or cyclopentadiene and an electrophile. A new fulvene derivative was prepared by converting a bromoketone as a starting material into a lithium salt of a ketal derivative and then reacting with an aldehyde or ketone to be reacted. In addition, there is only one bridge carbon of the metallocene catalyst based on the fulvene derivative having a substituent at the 2,5 positions thus prepared, and the substituent is only substituted at the alpha position with respect to the bridge position carbon of the cyclopentadienyl ligand derived from fulbene. The metallocene catalyst which had it was able to be manufactured. In particular, in Examples 3 to 9, the metallocene catalyst having a substituent only at the alpha position of the cyclopentadienyl group has good activity and copolymerizability for copolymerization of cyclic olefins such as norbornene having a high steric hindrance during polymerization. As shown in FIG. 2, the activity of the cyclic olefin copolymer (COC) was better than that of the polymerization using the isopropylene 9-fluorenylcyclopentadienyl zirconium dichloride catalyst used in Comparative Examples 2 to 4.

As described above, the metallocene catalyst prepared according to the present invention is a cyclic olefin because it has less steric hindrance and at the same time has a higher electronic effect than the metallocene catalyst prepared using a fulvene derivative obtained by a conventional method. It can be advantageously used for the copolymerization of large monomers such as copolymers (COC).

Claims (15)

A compound represented by the following formula (5): [Formula 5] In the formula (5), R ₁ , R ₂ , R ₃ and R ₄ are each independently or simultaneously hydrogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Alkyl or aryl having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₃ and R ₄ may be linked to one another in a ring by an alkylidine radical comprising an alkyl or aryl radical; A is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Indenyl or derivatives thereof; Substituted or unsubstituted amido groups; Or a substituted or unsubstituted phosphino group. The compound of claim 1, wherein R ₁ and R ₂ are methyl, one or both of R ₃ and R ₄ is phenyl, and A is fluorenyl or a derivative thereof. Metallocene catalyst represented by the following formula (1): [Formula 1] In the formula of Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are each independently or simultaneously hydrogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Alkyl or aryl having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₃ and R ₄ may be linked to one another in a ring by an alkylidine radical comprising an alkyl or aryl radical; M is a Group 4 transition metal; A is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Indenyl or derivatives thereof; Substituted or unsubstituted amido groups; Or a substituted or unsubstituted phosphino group; And Q ₁ and Q ₂ are each independently or simultaneously halogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Substituted or unsubstituted alkylidene having 1 to 20 carbon atoms; Substituted or unsubstituted amido groups; Alkylalkoxy having 1 to 20 carbon atoms; Or an aryl alkoxy group. According to claim 3, wherein the metallocene catalyst of formula (1) is a metal A is a fluorenyl or derivatives thereof, R ₁ , R ₂ , R ₃ and R ₄ are alkyl or aryl radicals having 1 to 20 carbon atoms at the same time Sen catalyst. 5. The metallocene catalyst of claim 4, wherein the metallocene catalyst of Formula 1 is R ₁ and R ₂ are methyl and R ₃ and R ₄ are phenyl in either or both cases. The metallocene catalyst of claim 3, wherein the metallocene catalyst of Formula 1 is A is indenyl or a derivative thereof, and R ₁ , R ₂ , R _3, and R ₄ are alkyl or aryl having 1 to 20 carbon atoms at the same time. . According to claim 3, wherein the metallocene catalyst of formula (1) is a substituted or unsubstituted amido group A, R ₁ , R ₂ , R ₃ And R _{4 It} is a metal to C 1-20 alkyl or aryl at the same time Sen catalyst. According to claim 3, wherein the metallocene catalyst of Formula 1 is a substituted or unsubstituted phosphino group A, R ₁ , R ₂ , R ₃ and R ₄ is a metal having 1 to 20 carbon atoms or alkyl at the same time Rosene catalyst. a) preparing a compound represented by the following Chemical Formula 5 by reacting a fulvene compound represented by the following Chemical Formula 7 with a cyclopentadiene derivative; And b) preparing a metallocene catalyst according to claim 3 comprising the step of preparing a compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 5 with the compound represented by Chemical Formula 6. [Formula 5] [Formula 6] M (Q ₁ ) (Q ₂ ) [Formula 7] In Formula 5, Formula 6 and Formula 7, R ₁ , R ₂ , R ₃ and R ₄ are each independently or simultaneously hydrogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Alkyl or aryl having 1 to 20 carbon atoms containing an oxygen atom or a nitrogen atom; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl, wherein R ₃ and R ₄ may be linked to one another in a ring by an alkylidine radical comprising an alkyl or aryl radical; M is a Group 4 transition metal; A is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Indenyl or derivatives thereof; Substituted or unsubstituted amido groups; Or a substituted or unsubstituted phosphino group; And Q ₁ and Q ₂ are each independently or simultaneously halogen; Alkyl, alkenyl, alkylaryl, or arylalkyl having 1 to 20 carbon atoms; Aryl; Substituted or unsubstituted alkylidene having 1 to 20 carbon atoms; Substituted or unsubstituted amido groups; Alkylalkoxy having 1 to 20 carbon atoms; Or an aryl alkoxy group. The method of claim 9, wherein A in Formula 5 is cyclopentadienyl or a derivative thereof; Fluorenyl or derivatives thereof; Or indenyl or a derivative thereof. delete delete delete delete delete