KR100458600B1 - Method for preparing olefin-cyclic olefin copolymer using methylene bridged metallocene catalyst - Google Patents

Abstract

The present invention relates to a method for preparing a copolymer of an olefin-cyclic olefin using a metallocene catalyst, wherein an ethylene and a cyclic olefin, or an alpha olefin and a cyclic olefin are two carbon atoms between two cyclopentadienyl groups. The methylene bridge, which is bridged to and has a large angle between the cyclopentadienyl groups and has a substituent only at the alpha position relative to the bridge position of the cyclopentadienyl group, increases the activity of the catalyst by the electronic effect and has the least steric hindrance. It provides a method for producing an olefin-cyclic olefin copolymer comprising the step of polymerizing under a metallocene catalyst.

Description

METHODS FOR PREPARING OLEFIN-CYCLIC OLEFIN COPOLYMER USING METHYLENE BRIDGED METALLOCENE CATALYST}

The present invention relates to a method for producing a copolymer of an olefin and a cyclic olefin, and more particularly to a method for producing an olefin-cyclic olefin copolymer using a metallocene catalyst.

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 properties 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. In addition, by changing the substituent of the cyclopentadienyl ligand, it is possible to control the stereoselectivity of the polymer when polymerizing the alpha olefin (Angew. Chem. Int. Ed. Engl. 1995, 34, 1143), When copolymerizing, the degree of copolymerization, molecular weight, distribution of second monomer, and the like may be controlled (US Pat. No. 5,470,811).

Catalysts suitable for the production of ethylene and alpha olefin copolymers LLDPE, VLDPE, EPM, EPDM and ethylene and alpha olefin and cyclic olefin copolymers, cyclic olefin copolymers (COC), ethylene and alpha olefin and styrene copolymers. Efforts to find are constantly being made. 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. Since metallocene catalysts are more expensive than conventional Ziegler-Natta catalysts, their activity is good economic value. If the reactivity to the second monomer is good, a polymer containing a large amount of the second monomer can be obtained even by the addition of a small amount of the second monomer, which is advantageous in various aspects in the polymerization process.

Several researchers have studied various catalysts and found that bridged catalysts generally have good reactivity with the second monomer. As a remedy, 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 bridged catalyst requires only a ratio of ethylene to hexene of 0.004 to 0.005, Catalysts require a ratio of 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.

Many studied bridged catalysts can be classified into three types depending on the type of bridge. -CR ₂ CR ₂ - is a silicon bridged catalyst that is connected by a - two cyclo-pentadienyl ligand is linked ethylene bridged catalyst, -CR ₂ - by a methylene bridged catalyst, connected by -SiR _2. Representative synthesis methods of these are shown in Schemes 1 to 3 below.

Scheme 1

Ethylene bridged catalyst

Scheme 2

silicon bridged catalyst

Scheme 3

Methylene bridged catalyst

The two cyclopentadienyl rings of the bridged catalyst can be variously loaded with various substituents 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. In view of the reason, the conventional method for synthesizing bridged ligands is because the cyclopentadienyl anion having a substituent is synthesized by nucleophilic attack on ethylenedibromide, dialkylsilicone dichloride or fulven. At this time, due to the steric hindrance effect, the substituent is mainly moved to the beta position relative to the bridge position in the cyclopentadienyl group. Attacking cyclopentadienyl anions with two substituents at positions 1 and 3 results in ligands having substituents at the alpha and beta positions, but no ligands having substituents at the alpha position.

In order to solve this problem, a new method for synthesizing a catalyst having a substituent only at the alpha position of a cyclopentadienyl group, which is difficult to synthesize in the related art, can be found in Korean Patent Laid-Open Publication No. 1998-025280.

Metallocene catalysts having substituents only at the alpha position of the cyclopentadienyl group have advantages in several respects. The portion where the monomers enter and the polymer grows is on the other side of the bridge, i.e., in the beta position relative to the bridge position in the cyclopentadienyl group. Since the catalyst 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. The least steric hindrance catalysts are bridges only and no substituents at all. However, these catalysts generally have low activity and poor copolymerization. This is because not only the steric hindrance effect acts on the catalyst but also the electronic effect on the catalyst activity and copolymerizability. Therefore, if the substituent which gives an electron such as an alkyl group with little steric hindrance effect can be substituted in the cyclopentadienyl ring, the activity and copolymerizability may be increased.

However, practically no such catalysts have been used to prepare copolymers of olefins and cyclic olefins.

Accordingly, an object of the present invention is to provide a method for preparing an olefin-cyclic olefin copolymer using a catalyst having excellent copolymerizability and polymerization activity, in consideration of the problems of the prior art.

It is another object of the present invention to bridge between two cyclopentadienyl groups with one carbon to increase the angle between the cyclopentadienyl groups, and to substitute a substituent only at the alpha position with respect to the bridge position of the cyclopentadienyl group. It is to provide a method for producing an olefin-cyclic olefin copolymer (COC) using a metallocene catalyst, which has a design having the least steric hindrance while increasing the activity of the catalyst by the electronic effect.

In order to achieve the above object, the present invention provides a method for producing an olefin-cyclic olefin copolymer (COC),

Ethylene and cyclic olefins, or alpha and cyclic olefins

It provides a preparation method comprising the step of polymerization under a methylene bridged metallocene catalyst represented by the formula (1).

[Formula 1]

In the formula of Formula 1,

M is a Group 4 transition metal,

Each R is the same or a metalloid radical of a Group 14 metal substituted with a hydrogen radical, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, or hydrocarbyl,

A and A 'are each substituted with the same or different hydrogen radicals, alkyl radicals of 1 to 20 carbon atoms, alkenyl radicals, aryl radicals, alkylaryl radicals, arylalkyl radicals, or hydrocarbyl, which may be attached to the bridging carbon. It is metalloid of group metal,

Q is the same or different halogen radical, each is an alkyl radical of 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical or an alkylidene radical of 1 to 20 carbon atoms.

Hereinafter, the present invention will be described in detail.

In the present invention, two cyclopentadienyl groups are bridged by one carbon to increase the angle between the cyclopentadienyl groups, and have a substituent only at the alpha position relative to the bridge position of the cyclopentadienyl group. The effect is to produce a copolymer of olefins and cyclic olefins (COC) using a catalyst designed to increase the activity of the catalyst while having the least steric hindrance.

In the metallocene catalyst having a substituent only in the alpha position, the bite angle between the two cyclopentadienyl groups is different depending on the number of bridged elements (mostly carbon or silicon). The opening angle between the cyclopentadienyl groups can be much larger than when there is only one carbon in the bridge position of the bridged metallocene catalyst. The more the angle between the cyclopentadienyl groups is wider, the higher the concentration of norbornene in the bulky state is, since the more monomer is inserted into the space of the catalyst in the copolymerization of the monomer such as the larger norbornene and the olefin. This will be easy.

Thus, when the metallocene catalyst having a large gap between the central metal and the cyclopentadienyl group has a property of having a substituent only at the alpha position, the steric hindrance of the substituent is minimal and the interaction between the monomer and the catalyst is the easiest. Because of this system, the activity of the polymerization reaction can be increased.

The method for synthesizing the methylene bridged metallocene catalyst of the present invention follows the following Scheme 4.

Scheme 4

In Scheme 4, each of A, A ', and R is the same as defined in Formula 1.

From 1,5-pentadiyne compounds with or without substituents at position 3 which can be obtained by basic organic reactions (manufactured by Lamber Brandsma, Preparative Acetylenenic Chemistry, 2d ed., Elsvier) Various transition metals can be used to obtain the compound of formula I described in Scheme 4 above. In particular, it may be economical to carry out a cyclization reaction under carbon monoxide pressure using a triple bond compound, norbornadiene as a raw material, and may be prepared using a single equivalent of Group 4, Group 8, Group 9 and Group 10 transition metals. Preferably it is prepared under carbon monoxide pressure using a catalytic amount of a Group 4 or Group 9 transition metal. Examples of cobalt compounds include octacarbonyldicobalt, or compounds in which some carbon monoxide is substituted by phosphine or phosphine oxide, dodecarbonyltricobalt, or compounds in which some carbon monoxide thereof is substituted by phosphine or phosphine oxide. , Co (acac) ₂ or Co (acac) ₃ activated by NaBH ₄ may be used.

The reaction for preparing the compound of formula II from the compound of formula I described in Scheme 4 is generally known as a conjugated addition reaction or a Michael addition reaction, which reacts with various organometallic compounds. (P. Perlmutter, Conjugate Addition Reaction in Organic Synthesis, Pergamon Press). Organic magnesium compounds, organic lithium compounds, organic zinc compounds, organic manganese compounds and the like can be used in various ways. It is preferable to use an organic copper compound alone or a mixture with an organic lithium or organic magnesium compound. More preferably, R ₂ CuLi obtained by mixing a copper halide monovalent compound and 2 equivalents of an organolithium compound may be used, and more preferably, a daily equivalent of an organolithium or organoaluminum compound with a catalytic amount of copper monovalent compound. Can be used. Hydrogen radicals may be incorporated into the aluminum hydrogen compound or the boron hydrogen compound.

The process for preparing the compound of the formula III from the compound of the formula II described in Scheme 4 is generally known as a reverse diels alder reaction and can be prepared by instantaneous contact with high temperature (Synthesis Communications, 9 (1), 41-). 47 (1997); Journal of American Chemical Society, 1971, 3091). The reaction may be carried out by contacting at 50 to 900 ° C. for 0.1 seconds to 1 hour. However, the reaction temperature is preferably 150 to 170 DEG C, and the reaction time is 1 second to 20 minutes. Removing the cyclopentadiene produced as a byproduct by vacuum during the reaction is advantageous for the reaction, and treating the compound of formula III produced during the reaction at low temperature by vacuuming the product does not last long at high temperature. This change can be prevented, which is good for improving the yield.

The method for preparing the compound of formula IV from the compound of formula III described in Scheme 4 can be obtained by nucleophilic attack of the organometallic compound on the ketone followed by acid treatment. As the organometallic compound, various kinds are possible, but the organolithium compound, the organo magnesium compound, and the organocerium compound are the easiest. Hydrogen radicals may also be incorporated into aluminum or boron hydrogen compounds. Treatment of the acid to remove water from the alcohol compound obtained by treating the organometallic compound is a conventional method, or iodine may be used instead of the acid, and heat is applied by removing the water by vacuum or a drying agent such as anhydrous magnesium sulfate. It can also react.

Preparation of the methylene bridged metallocene compound represented by Formula 1 from the compound of Formula IV described in Scheme 4 is possible by various methods reported in the literature, and typically, two equivalents of normal-butyllithium are treated. To form a cyclopentadienyl anion in cyclopentadiene, which can be obtained by reaction with a metal halide compound or the like.

The methylene bridged metallocene compound represented by the formula (1) having only one carbon at the bridge position and having a substituent only at the alpha position as a catalyst, and as a promoter is a compound represented by the following formula (2) At least one selected from the group consisting of a compound, a compound represented by the formula (4a) and a compound represented by the formula (4b) can be used for polymerization of the olefin. In addition, such promoters may be used in a form supported on silica or alumina, like the metallocene catalyst of Formula 1.

[Formula 2]

-[Al (R ⁵ ) -O] _α-

In the formula (2),

Each R ⁵ is independently or simultaneously a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms, optionally substituted with halogen, and α is an integer of 2 or more, and the compound may be present in linear, circular or mesh form .

[Formula 3]

N (R ⁵ ) ₃

In the formula (3),

N is aluminum or boron,

Each R ⁵ is independently or simultaneously a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms, optionally 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 an element of group 13 on the periodic table, for example aluminum or boron,

E is an aryl radical having 6 to 20 carbon atoms, and includes a halogen radical, a hydrocarbyl having 1 to 20 carbon atoms, alkoxy, phenoxy radical, nitrogen, phosphorus, sulfur, or a hydrocarbyl radical having 1 to 20 carbon atoms including an oxygen atom. One or more substituted, four E may be the same or different from each other.

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

Examples of the compound (alkyl metal compound) represented by Formula 3 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, and tri-s-butylaluminum , 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.

In addition, examples of the compound represented by Formula 4a or Formula 4b 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 tetra Phenylaluminum, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p -Dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N- Diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, tri Phenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, Trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) boron, triethylammonium tetra (o, p-dimethylphenyl ) Boron, trimethyl ammonium tetra (o, p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethyl ammonium tetra (p-trifluoromethylphenyl) boron, tributyl ammonium Tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, di Ethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, triphenyl carbonium tetra (p-tripulomethylphenyl) boron, triphenyl carbonium tetrapentafluorophenyl boron, and the like.

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.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Organic reagents and solvents necessary for the preparation of the catalyst were purchased from Aldrich and Merck and purified by standard methods. 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, spectra were obtained by dissolving in CDCl ₃ solvent using 300 MHz Bruker nuclear magnetic resonance (NMR).

Preparation Example 1

(Catalyst manufacture)

(Methylene Bis (1,4-dimethylcyclopentadienyl) zirconium dichloride (Synthesis of Compound Represented by Formula 1)

1) 4,4'-methylenebis (tricyclo [5.2.1.0] deca-4,8-dien-3-one (I): 1,5 pentadiene dissolved in tetrahydrofuran as starting material A yield of 50% was obtained by the method described in Synthesis 1998, 142.

The NMR analysis results are as follows.

¹ H NMR (CDCl ₃ ): 7.26 7.23 (m, 2H), 6.28 (dd, 2H), 6.20 (dd, 2H), 3.07 (s, 2H), 2.90 (s, 2H), 2.72 (s, 2H), 2.68 (s, 2H), 2.28 (d, 2H), 1.37 (d, 2H), 1.17 (d, 2H) ppm

2) Preparation of 4,4'-methylenebis (5-methyltricyclo [5.2.1.0] deca-8-dien-3-one (II)

4.7 g of dry CuI is placed in a Schlenk flask and 100 ml of diethyl ether is added thereto. Slowly add 33 ml of 1.4 M methyllithium dissolved in diethyl ether at -5 ° C. After about 1 hour the temperature was lowered to -78 ° C and 3.0 g of the compound of formula I were instantaneously added. Slowly raise the temperature to room temperature and stir overnight. Add the ammonium chloride solution to the ammonia water, add an aqueous solution with an acidity of about 9, and collect the ether layers with a separatory funnel. After stirring with anhydrous magnesium sulfate, the filter was removed to remove moisture from the ether layer, and the ether was removed by a vacuum evaporator under reduced pressure. When the reaction degree was confirmed by NMR, almost no compound of structure II was formed without side reaction, and the yield was obtained as 85%.

The NMR analysis results are as follows.

¹ H NMR (CDCl ₃ ): 6.17 (dd, 2 H), 6.12 (dd, 2 H), 3.11 (s, 2 H), 2.73 (s, 2 H), 2.55 2.40 (m, 2H), 2.31 (d, 2H), 1.99 (dt, 1H), 1.84 (dd, 2H), 1.38 (d, 2H), 1.40 1.26 (m, 3H), 1.28 (s, 6H), 1.02 ( d, 2 H) ppm

3) 2,2'-methylenebis (3-methyl-2-cyclopenten-l-one (III)

1.5 g of the compound of formula II obtained above is placed in an open quartz tube. One end is connected to an open glass tube with a hose, the glass tube is immersed in a flask and flask containing liquid nitrogen, and the crystal tube containing the compound of formula II is placed in a furnace made of Lindbergh controlled at 420 ° C. Leave for 2 minutes 30 seconds. The crystal tube was removed from the furnace, cooled to room temperature, and the contents were purified by silica gel column chromatography with a 1: 1 mixture of ethyl acetate: hexane to obtain 0.6 g of the pure compound of formula III in 66% yield.

The NMR analysis results are as follows.

¹ H NMR (CDCl ₃ ): 3.05 (s, 2 H), 2.5 2.4 (m, 4 H), 2.35 2.25 (m, 4 H), 2.18 (s, 6 H) ppm

4) 2,2'-methylenebis (1,3-dimethyl-1,3-cyclopentadiene (IV)

1.23 g of the compound of formula III prepared above is placed in a Schlenk flask and 50 ml of anhydrous tetrahydropurine (THF) is added. Soak in -78 ° C low temperature bath and add 12 ml of 1.5M MeLi dissolved in ether with stirring. Slowly raise the temperature to room temperature and stir overnight. The reaction is poured into a separatory funnel containing concentrated aqueous ammonium chloride solution and extracted by adding ethyl acetate. The organic layers are collected separately to remove all solvents with a reduced pressure circulating evaporator. Dissolve the product in 120 ml ethyl acetate and place it in a separatory funnel containing 120 ml 2 N hydrochloric acid solution. Shake and mix for 4 minutes. Remove the hydrochloric acid solution from the lower layer and wipe it off with concentrated NaHCO ₃ solution to remove all the hydrochloric acid dissolved in the ethyl acetate layer. The residual moisture of the ethyl acetate layer was removed with anhydrous magnesium sulfate, and then the solvent was removed with a reduced pressure circulation evaporator. 0.77 g of Compound IV was obtained by silica gel column chromatography using a solvent in which hexane and benzene were mixed at a volume ratio of 10: 1 (yield 63%).

The NMR analysis results are as follows.

¹ H NMR (CDCl ₃ ): 5.80 (s, 2 H), 3.27 (s, 2 H), 2.76 (s, 4 H), 1.93 (s, 6 H), 1.82 (s, 6 H) ppm

5) methylene bis (1,4-dimethylcyclopentadienyl) zirconium dichloride (Formula 1)

0.77 g of the compound of the formula IV prepared above and 30 ml of anhydrous ether were added to a Schlenk flask, and the temperature was lowered to −78 ° C., and 3.1 ml of 2.5 M n-BuLi dissolved in hexane was added. Raise slowly to room temperature and stir for 4 hours. The obtained solid compound was washed with ether, and then all solvents were removed by a vacuum pump. Toluene 30 ml was added, 0.78 g of ZrCl ₄ was added to a dry box, followed by stirring at room temperature. Filtering the product to remove toluene under vacuum yielded a pure compound catalyst of formula 1 at a yield of 20%.

The NMR analysis results are as follows.

¹ H NMR (CDCl ₃ ): 6.45 (s, 4 H), 4.07 (s, 2 H), 2.21 (s, 12 H) ppm

Preparation Example 2

(Catalyst manufacture)

Ethylenebis (1,4-dimethylcyclopentadienyl) zirconium dichloride was prepared according to Korean Patent Publication No. 1998-025280.

Example 1

(Copolymerization of Ethylene and Norbornene)

Norbornene is dissolved in toluene to make a 56% by weight solution and 200 ml is placed in a pressure reactor. 1.8 ml of methylaluminoxane (6.9 wt% Al of toluene solution, density = 0.88 c / ml, manufactured by Akzo) was added thereto. The reactor is 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 compound of Formula 1 (1 μM concentration, toluene solution), which is the catalyst prepared in Preparation Example 1, was added to the reactor, and then rapidly stirred at 200 rpm while ethylene pressure was added at 60 psig. After 20 minutes, the contents are poured into acetone solution to separate the white solid compound. The solvent was removed by filtration, acetone was added and stirred at room temperature overnight, followed by filtration to obtain a white solid polymer. This was dried under reduced pressure in vacuo to obtain 38.19 g of copolymer. Tg was checked at 228 ° C. using DSC.

Comparative Example 1

Ethylene bridged ethylene bis (1,4-dimethylcyclopentadienyl) zirconium dichloride catalyst prepared by the copolymerization of ethylene and norbornene under the same method and conditions as in Example 1, but using the polymerization catalyst Polymerization was carried out. The amount of catalyst (1 μM concentration, toluene solution) was used 2 ml to obtain 14.9 g of copolymer. Tg was checked at 198 ° C. using DSC.

Comparative Example 2

The copolymerization of ethylene and norbornene was carried out in the same manner and in the same manner as in Example 1, except that an isopropylene 9-florenylcyclopentadienyl zirconium dichloride catalyst commercially available from Boulder was used as a polymerization catalyst. The amount of the catalyst (1 μM concentration, toluene solution) was used in 2 ml to obtain 12.8 g of copolymer. Tg was confirmed at 176 ° C. using DSC.

Example 2

The polymerization was carried out by reducing the amount of catalyst to 1 ml in the same manner and in the same manner as in Example 1. 23 g of copolymer were obtained and Tg was checked at 226 ° C. using DSC.

Example 3

The polymerization was carried out by increasing the amount of catalyst to 4 ml by the same method and conditions as in Example 1. 51.41 g of copolymer were obtained and Tg was checked at 252 ° C. using DSC.

Example 4

In the same manner and in the same manner as in Example 1, the polymerization was carried out at a reaction temperature of 30 ° C. 11.6 g of copolymer were obtained and Tg was checked at 199 ° C. using DSC.

Example 5

In the same manner and in the same manner as in Example 1, the polymerization was carried out at a reaction temperature of 100 ° C. 36.87 g of copolymer were obtained and Tg was checked at 250 ° C. using DSC.

Example 6

The polymerization was carried out in the same manner and in the same manner as in Example 1 with a reaction pressure of 30 psig. 15.65 g of copolymer were obtained and Tg was checked at 251 ° C. using DSC.

Example 7

In the same manner and in the same manner as in Example 1, the polymerization was carried out at a reaction pressure of 50 psig. 32.6 g of copolymer were obtained and Tg was checked at 238 ° C. using DSC.

Example 8

In the same manner and in the same manner as in Example 1, the polymerization was carried out at a reaction pressure of 100 psig. 52.83 g of copolymer were obtained and Tg was checked at 226 ° C. using DSC.

Example 9

3.6 ml of methylaluminoxane was added and polymerized in the same manner and in the same manner as in Example 2. 33.26 g of copolymer were obtained and Tg was checked at 228 ° C. using DSC.

Example 10

0.9 ml of methylaluminoxane was added and polymerized in the same manner and in the same manner as in Example 1. 29.53 g of copolymer were obtained and Tg was checked at 235 ° C. using DSC.

Example 11

3.6 ml of methylaluminoxane was added and polymerized in the same manner and in the same manner as in Example 1. 37.18 g of copolymer were obtained and Tg was checked at 221 ° C. using DSC.

Example 12

0.9 ml of methylaluminoxane was added and polymerized in the same manner and in the same manner as in Example 3. 46.75 g of copolymer were obtained and Tg was checked at 242 ° C. using DSC.

Example 13

3.6 ml of methylaluminoxane was added and polymerized in the same manner and in the same manner as in Example 3. 44.48 g of copolymer were obtained and Tg was checked at 252 ° C. using DSC.

In the above embodiment, the metallocene catalyst having one carbon-linked bridge of the present invention increases the angle of opening of each cyclopentadienyl moiety, thereby facilitating interaction of the monomer with the catalyst during the polymerization process. It can be seen that the activity is much better in the copolymerization of ethylene and cyclic olefin than the catalyst having two or more carbon bridges used in Comparative Example 1. In addition, the present catalyst having a substituent only at the alpha position shows good activity and copolymerizability for the copolymerization of cyclic olefins such as norbornene having a high steric hindrance, and isopropylene 9-florenylcyclopentadienyl zir used in Comparative Example 2 It showed better activity for the production of cyclic olefin copolymers (COC) than when polymerized with a conium dichloride catalyst.

When copolymerizing an olefin and a cyclic olefin, the angle between the two cyclopentadienyl groups is bridged by a single carbon and the cyclopentadienyl group has a large angle, and the substituent is only at the alpha position relative to the bridge position of the cyclopentadienyl group. When the methylene bridged metallocene compound designed to increase the activity of the catalyst and reduce steric hindrance by the electronic effect is used as a catalyst, a copolymer of olefin and cyclic olefin is produced with excellent copolymerization and high activity. can do.

Claims (5)

In the method for producing an olefin-cyclic olefin copolymer (COC), Ethylene and cyclic olefins, or alpha and cyclic olefins A preparation method comprising the step of polymerizing under a methylene bridged metallocene catalyst represented by Formula 1 below: [Formula 1] In the formula of Formula 1, M is a Group 4 transition metal, Each R is the same as or different from each other and is a metalloid radical of a Group 14 metal substituted with a hydrogen radical, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, or hydrocarbyl, A and A 'are each independently or simultaneously a metalloid of a Group 14 metal substituted with a hydrogen radical, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical, or hydrocarbyl ego, Each independently or simultaneously is a halogen radical, an alkyl radical having 1 to 20 carbon atoms, an alkenyl radical, an aryl radical, an alkylaryl radical, an arylalkyl radical or an alkylidene radical having 1 to 20 carbon atoms. The method of claim 1, In the methylene bridged metallocene catalyst represented by Formula 1, A and A 'in Formula 1 are hydrogen, and each R is the same radical. The method of claim 1, In the methylene bridged metallocene catalyst represented by Formula 1, A and A ′ in Formula 1 are hydrogen, and each R is methyl. The method of claim 1, The polymerization is at least one selected from the group consisting of linear, circular, or mesh-type compounds represented by the following Chemical Formula 2, compounds represented by the following Chemical Formula 3, compounds represented by the following Chemical Formula 4a, and compounds represented by the following Chemical Formula 4b. The method of preparation carried out further comprising the promoter selected: [Formula 2] ^{- [Al (R 5) -O} ] a - In the formula (2), Each R ⁵ is independently or simultaneously a halogen radical or a hydrocarbyl radical having 1 to 20 carbon atoms, optionally substituted with halogen, a is an integer of 2 or more, [Formula 3] N (R ⁵ ) ₃ In the formula (3), N is aluminum or boron, Each R ⁵ is independently or simultaneously a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, optionally substituted with halogen, [Formula 4a] [LH] ⁺ [NE ₄ ] ^- [Formula 4b] [L] ⁺ [NE ₄ ] ^- In the 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, The four Es, each independently or simultaneously, consist of a halogen radical, hydrocarbyl having 1 to 20 carbon atoms, a hydrocarbyl radical having 1 to 20 carbon atoms containing nitrogen, phosphorus, sulfur, or oxygen atoms, alkoxy, and phenoxy radicals An aryl radical having 6 to 20 carbon atoms substituted with at least one substituent selected from the group. The method of claim 1, The catalyst is a catalyst supported on a silica or alumina carrier.