KR20150084733A - Method for preparing copolymer comprising ethylene, propylene and diene using multi-metallic organometallic catalysts - Google Patents

Abstract

Disclosed are a multi-metallic metallocene compound and an olefin polymerized catalyst containing the same. More particularly, the multi-metallic metallocene compound contains, as central metals, at least two metals which belong to the third to tenth rows in the periodic table, and those metals are connected by bridging ligands including hetero electrons and aromatic groups, which is an organometallic compound. The olefin polymerized catalyst uses the multi-metallic metallocene compound as a main catalyst, and an aluminoxane compound, organoaluminum compound, or boron-based compound as a co-catalyst, which is used as a catalyst when manufacturing ethylene, alpha-olefin, and diolefin copolymer. Therefore, molecular weight and distribution of the molecular weight are controllable, allowing very high molecular weight of copolymers to be obtained.

Description

TECHNICAL FIELD The present invention relates to a method for preparing a copolymer containing ethylene, propylene and a diene using a multimetal metallocene compound,

The present invention relates to a multimetal metallocene compound and an olefin polymerization catalyst system comprising the same.

Conventionally, the so-called Ziegler-Natta catalyst systems, which consist of the main catalyst components of titanium or vanadium compounds and the cocatalyst components of alkylaluminum compounds, have been used to prepare copolymers with ethylene and alpha-olefins. However, although the Ziegler-Natta catalyst system exhibits high activity for ethylene homopolymerization, the copolymerization reactivity with the higher alpha-olefin is poor due to the non-uniform catalytic activity point, and therefore, a large amount of alpha-olefin is required for the copolymerization of ethylene and alpha- An olefin comonomer should be used and the catalyst activity is lowered under such conditions.

Recently, a so-called metallocene catalyst system comprising a metallocene compound of Group 4 transition metal such as titanium, zirconium, and hafnium and a promoter, methylaluminoxane, has been developed. Since the metallocene catalyst system is a homogeneous catalyst having a single catalyst activity point, it is possible to produce a copolymer of ethylene and alpha-olefin having a narrow molecular weight distribution and uniform composition distribution as compared with the conventional Ziegler-Natta catalyst system Have.

On the other hand, a so-called geometrically constrained non-metallocene catalyst system in which a transition metal is linked in a ring form as a catalyst capable of producing a polymer having high catalytic activity and high molecular weight in the copolymerization of ethylene and an alpha-olefin under solution polymerization conditions has been disclosed. EP 0416815 and EP 0420436 disclose examples in which an amide group is linked in the form of a ring to one cyclopentadiene ligand. In EP 0842939, a phenol-based ligand is used as an electron donor compound in combination with a cyclopentadiene ligand An example of a catalyst in the form of a ring is shown. However, in the case of these geometric constrained catalysts, the reactivity with the higher alpha-olefins was significantly improved due to the lowered steric hindrance effect of the catalyst itself. However, since the catalyst synthesis step is complicated and the yield of the ring-forming reaction process between the ligand and the transition metal compound is very low, it may be difficult to realize an economical production process suitable for the copolymerization of ethylene and alpha-olefin.

On the other hand, an example of a non-metallocene catalyst system that is not geometrically constrained is disclosed in U.S. Patent No. 6,239,238. In this patent, it can be seen that the single-site catalyst using at least one phosphine-imine compound as a ligand exhibits a high ethylene conversion in ethylene and alpha-olefin copolymerization at high temperature solution polymerization conditions of 140 ° C or higher. However, these catalysts are not highly reactive with high alpha-olefins as in the case of metallocene catalyst systems and may not be suitable for preparing polymers of ethylene and high alpha-olefins.

Polymers with narrow molecular weight distributions and compositional distributions polymerized using these single-screw catalyst systems have a higher molecular weight distribution with polymerized molecular weight distribution using Ziegler-Natta catalysts and higher strengths than polymers with broad compositional distributions, There is an advantage that the stickiness phenomenon can be reduced when the product is manufactured. However, when the molecular weight distribution of the polymer is narrow, it is difficult to process and has a disadvantage that a large amount of energy is required. Accordingly, research and development on a multi-nuclear metallocene catalyst system to overcome the disadvantage of narrow molecular weight distribution of such polymers has been carried out all over the world.

Specifically, for example, the following.

U.S. Patent No. 5,525,678 discloses a catalyst system for polymerization of binuclear olefins in which a metallocene compound and a non-metallocene compound are simultaneously supported on a support to polymerize a high molecular weight polymer and a low molecular weight polymer simultaneously Lt; / RTI > However, this catalyst system is required to carry the metallocene compound and the non-metallocene compound separately, and the process is complex such that the carrier is pretreated with various compounds for the support reaction.

In addition, U.S. Patent No. 5,700,886 discloses a method of controlling the molecular weight distribution of a polymer by adding two or more metallocene compounds as catalysts to a reactor and polymerizing the same to prepare a metallocene compound having a complex structure There is a disadvantage that the polymerization cost is high during the production of the polymer and that the polymerization conditions are strictly controlled in order to obtain a polymer having a desired molecular weight distribution.

In addition, U.S. Patent No. 5,753,577 discloses that a chemical bond exists directly between the central metal while a Group 4 element having a trivalent oxidation number is used as a central metal, and a bond is also present between ligands bonding to the center metal A double-nuclear metallocene compound is disclosed, and when the polymer is polymerized using this catalyst, there is a disadvantage in that the molecular weight of the resulting polymer is low.

In addition, U.S. Patent No. 5,442,020 discloses a process for producing a double-nucleated metallocene compound by reacting a cyclopentadienyl group linked with an alkylene group and a silylene group through a Group 4 metal compound to ethylene polymerization, propylene polymerization, (? -olefin) copolymerization. However, in the case of this catalyst, there is a problem that complex steps such as introduction of an alkylene group or a silylene group must be performed in the production of the catalyst.

In addition, U.S. Patent No. 5,627,117 discloses a process for producing a polyimide-based metal catalyst by reacting a cyclopentadienyl group, which is an alkylene group, a silylene group, or a divalent germanium (Ge) Discloses a method of polymerizing ethylene, propylene or ethylene with an alpha-olefin using a Rhodamine catalyst system. However, this catalyst has a problem in that it exhibits lower activity than a conventional catalyst when it is polymerized at a high temperature.

Also, U.S. Patent No. 6,010,974 discloses a method of polymerizing styrene using a double-nucleated metallocene compound produced by reacting a Group 4 metal compound with a cyclopentadienyl group linked through an alkylene group and a silylene group. However, the catalyst disclosed in this patent has disadvantages that can be used only when producing a styrene homopolymer or a styrene copolymer.

The present invention provides a multimetallic organometallic catalyst capable of producing a polymer by controlling the molecular weight and the molecular weight distribution in a homogeneous or heterogeneous phase, increasing the molecular weight of the polymer, and exhibiting excellent polymerization activity at a high temperature. Especially, in linking two independent polymerization active sites, electronically conjugated aryl groups are introduced and the two aryl groups are connected to hetero atoms such as oxygen, sulfur and nitrogen in the presence of a non-covalent electron pair, To provide a multimetallic organometallic catalyst that forms a conjugate structure between electron pairs to form charge distribution between two active sites while increasing fluidity of the bridge through heteroatoms.

In one embodiment of the present invention, there is provided a multimetal metallocene compound represented by the following general formulas (1) to (2).

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

M ₁ and M ₂ are the same or different and are a transition metal or a lanthanide metal of the group 3 to 10 having an oxidation number of +2 to +4,

A is a heteroatom other than carbon, selected from oxygen, nitrogen, sulfur and phosphorus,

Ar ₁ And Ar ₂ are independently (C6-C30) arylene groups,

R ₁ to R ₆ are, independently of each other, selected from the group consisting of hydrocarbyl, hydrocarbylsilyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbyl a A hydrocarbyloxy group which may be covalently bonded to each other to form one or two or more conjugated or non-conjugated rings,

Z ₁ and Z ₂ are independently of each other a functional group having two bonding sites,

Y ₁ and Y ₂ are independently a functional group having two bonding sites, Y ₁ is bonded to M ₁ and Z ₁ , Y ₂ is bonded to M ₂ and Z ₂ ,

Xn is an anion or a double anion ligand.

The multimetal metallocene compound according to a preferred embodiment of the present invention may be one wherein M ₁ and M ₂ are selected from Ti, Zr and Hf.

The metallocene compound of a metal-metal according to a preferred embodiment of the present invention are each a Z ₁ and Z ₂ independently ^{_{-SiR * 2 -, -CR * 2}} -, -GeR * 2 - or -BR ^* - (wherein, R ^* may be independently hydrogen, or selected hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl or halogenated aryl, with the exception of hydrogen having from 1 to 20 atoms to one another to form a cyclic structure).

The multimetal metallocene compound according to a preferred embodiment of the present invention is such that Y ₁ and Y ₂ are each independently -NR ^* -, -PR ^* -, -O- or -S-, wherein R ^* Hydrogen, or selected hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl or halogenated aryl having 1 to 20 atoms other than hydrogen).

The multimetal metallocene compound according to a preferred embodiment of the present invention is a compound in which X _n independently from each other are a halogen atom, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) ) alkyl, (C1-C20) alkoxy, (C3-C20) alkyl siloxy, (C6-C30) aryl siloxy, (C1-C20) alkylamino or (C6-C30) arylamino group, n is M ₁ and And may have a number of 0 to 4 depending on the oxidation number of M < ₂ >.

The multimetal metallocene compound according to a preferred embodiment of the present invention may be selected from compounds represented by the following formulas.

In a specific embodiment of the present invention, the multimetal metallocene compound is {4- [1- (Nt-butylamidodimethylsilyl) -2,3,4-trimethylcyclopentadienyl]] phenyl ether} {titanium di ₂ } or {4- [1- (Nt-butylamidodimethylsilyl) -3,4-dimethyl-cyclopentadienyl]] phenyl ether} {titaniumdichloride} ₂ .

An exemplary embodiment of the present invention provides an olefin polymerization catalyst system comprising a multimetal metallocene compound according to one of the above embodiments.

As a specific example, the olefin polymerization catalyst system may include a cocatalyst selected from an aluminoxane compound, an alkyl aluminum compound, and a boron compound, or a mixture thereof; . ≪ / RTI >

An exemplary embodiment of the present invention provides an olefin-based polymer obtained by using a multimetal metallocene compound as a catalyst according to the above embodiments.

The multimetal metallocene compound according to the present invention can be used as a catalyst in the production of ethylene, alpha-olefin and diolefin copolymer to control the molecular weight and molecular weight distribution of the polymer, There is a high commercial value.

The multimetal metallocene compound according to an embodiment of the present invention has two or more metals of Group 3 to Group 10 in the periodic table as a central metal and has a structure in which these metals are linked to each other by a bridging ligand containing a hetero atom and an aromatic group And specifically represented by the following formulas (1) and (2).

[Chemical Formula 1]

(2)

In the multimetal metallocene compounds represented by the general formulas (1) and (2), M ₁ and M ₂ , which are the same as or different from each other, are transition metals of Groups 3 to 10 in the periodic table having an oxidation number of +2 to +4, Titanium, zirconium or hafnium, more preferably titanium.

A may be selected from among oxygen, nitrogen, sulfur and phosphorus as a hetero atom excluding carbon, preferably oxygen or sulfur, more preferably oxygen.

Ar ₁ And Ar ₂ are each an arylene group of (C6-C30), which serves as a bridge connecting the heteroatom A and the cyclopentadienyl group, wherein the arylene group may be substituted or unsubstituted phenyl, Phenyl, naphthyl, anthracenyl, and preferably phenyl or biphenyl.

And R &_lt; ₁ > to R &_lt; ₆ &_gt; independently of each other are hydrogen or a group consisting of hydrocarbyl, hydrocarbylsilyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbyl (C1-C20) alkyl, (C6-C30) alkoxy, and (C6-C30) alkylthio groups, which may form one or two or more conjugated or nonconjugated rings, Aryl, (C2-C20) alkenyl and (C6-C30) aryl (C1-C20) alkyl to form a fused ring by forming a cyclic structure.

Z ₁ and Z ₂ is a functional group having two binding sites, each independently, specifically, ^{_{-SiR * 2 -, -CR * 2}} -, -GeR 2 - or -BR ^* -, preferably CR ^* ₂ - or -SiR ^* ₂ -, wherein R ^* is independently selected from hydrogen, or selected hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenated aryl having 1 to 20 atoms other than hydrogen, (C 1 -C 20) alkyl, (C 6 -C 30) aryl, (C 2 -C 20) alkenyl and (C 6 -C 30) aryl (C 1 -C 20) alkyl, To form a conjugated or non-conjugated cyclic structure.

Y ₁ and Y ₂ are each independently a functional group having two bonding sites, specifically, -O-, -S-, -NR ^* - or -PR ^* -, Y ₁ is a group having M ₁ and Z ₁ And Y < _{2 &gt}; M ₂ and Z ₂ , wherein R ^* is hydrogen or a selected hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl or halogenated aryl having 1 to 20 atoms other than hydrogen, specifically, (C 1 -C 20) alkyl, (C 6 -C 30) aryl, (C 2 -C 20) alkenyl, (C 3 -C 20) cycloalkyl and (C 6 -C 30)

Xn independently of one another are a halogen atom or an alkyl, cycloalkyl, alkoxy, aryl, aryloxy, alkylsiloxy, arylsiloxy, dialkylamino or diarylamino group having 1 to 20 atoms excluding hydrogen, and n May have a number of 0 to 4 depending on the oxidation number of M ₁ and M ₂ . More specifically, Xn independently of each other are selected from the group consisting of halogen atoms, (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6- ) alkyl siloxy, (C6-C30) aryl siloxy, (C1-C20) alkylamino or (C6-C30) arylamino group, n is one having a number of from 0 to 4 depending on the oxidation number of M ₁ and M ₂ .

Specifically, the multimetal metallocene compounds represented by the general formulas (1) and (2) may be represented by the following chemical formulas.

More specifically, the multimetal metallocene compound represented by the above general formulas (1) and (2) is a {4- [1- (Nt- butylamidodymethylsilyl) -2,3,4-trimethylcyclopentadienyl]] phenyl ether} (Titanium dichloride) ₂ or {4- [1- (Nt-butylamidodimethylsilyl) -3,4-dimethyl-cyclopentadienyl]] phenyl ether} {titaniumdichloride} ₂ .

The method for preparing the compound represented by the above general formulas (1) and (2) is not particularly limited. For example, the compound represented by the general formula (1) can be synthesized from a compound containing a hetero atom and an aromatic group, To synthesize the displayed compound.

(3)

In the above formula, A, Ar ₁ , Ar ₂ , R ₁ to R ₆ are as defined above.

Next, the compound of formula (3) is first reacted with a compound containing Z ₁ and Z ₂ radicals, and then a compound containing Y ₁ and Y ₂ radicals is reacted to prepare a compound represented by formula (4).

[Chemical Formula 4]

In the above formula, A, Ar ₁ , Ar ₂ , R ₁ to R _6, Z ₁ , Z ₂ , Y ₁ and Y ₂ are as defined above.

Finally, a compound represented by Formula 1 may be obtained by reacting a compound represented by Formula 4 with a metal compound.

An example of the methods described herein is one which illustrates one of the many possible ways of making the multimetal metallocene compound according to one embodiment of the present invention, and is not limited by this method.

According to another embodiment of the present invention, there is provided an olefin polymerization catalyst system comprising the multimetal metallocene compound represented by the general formulas (1) to (2).

Such a multimetal metallocene compound may be included as a main catalyst in an olefin polymerization catalyst system, and may contain an aluminoxane compound, an organoaluminum compound, or a boron compound as a cocatalyst.

Specifically, the transition metal catalyst of Formula 1 may be an active catalyst component used in olefin polymerization. Preferably, Xn ligand in the transition metal compound according to the present invention is extracted to cationize the center metal, An aluminoxane compound, an organoaluminum compound or a Bulky boron compound which can act as an ion, that is, an anion, or a mixture thereof can be used as a cocatalyst. The organoaluminum compound used in this reaction is to remove trace amounts of polar substances acting as catalyst poisons in the reaction solvent, but may act as an alkylating agent when the Xn ligand is halogen.

The aluminoxane compound that can be used as a cocatalyst in the olefin polymerization catalyst system according to an embodiment of the present invention is represented by Chemical Formula 5 and has a linear or cyclic or network structure and specifically includes methylaluminoxane, Hexanoic aluminoxane, octylaluminoxane, decylaluminoxane, and the like.

[Chemical Formula 5]

In the formula, R ₇ is an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 100.

Further, in the catalyst for polymerization of the present invention, the organoaluminum compound is represented by the following formula (6), and specific examples thereof include trimethylaluminum, triethylaluminum, tributylaluminum, trihexylaluminum, trioctylaluminum, Trialkylaluminum such as aluminum; Dialkyl aluminum alkoxide such as dimethyl aluminum methoxide, diethyl aluminum methoxide and dibutyl aluminum methoxide; Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride and dibutylaluminum chloride; Alkyl aluminum dialkoxides such as methyl aluminum dimethoxide, ethyl aluminum dimethoxide and butyl aluminum dimethoxide; Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride and butylaluminum dichloride, and the like.

[Chemical Formula 6]

The above formula, R _8, R ₉ and R ₁₀ are each the same or different as an alkyl group of C1 ~ 10, an alkoxy group or a halide group of C1 ~ 10, R _8, includes at least one alkyl group in R ₉ and R ₁₀ do.

Further, in the catalyst for polymerization of the present invention, the bulk-boron compound which reacts with the multimetal metallocene compound to cause the transition metal compound to have a catalytic activity is specifically exemplified by trimethylammonium tetraphenylborate, Tetramethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, anilinium tetraphenylborate, anilinium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, Borate, pyridinium tetraphenylborate (Pentafluorophenyl) borate, silver tetraphenyl borate, silver tetrakis (pentafluorophenyl) borate, pyridinium tetrakis (pentafluorophenyl) borate, pyridinium tetrakis Phenyl) borate, tris (pentafluorophenyl) borane, tris (3,4,5-trifluorophenyl) borane, and the like.

The bulky compounds that react with the aluminoxane compound, the organoaluminum compound, or the transition metal compound as the cocatalyst in the polymerization catalyst of the present invention to make the transition metal compound have catalytic activity are not limited to the above examples, Or mixtures thereof.

The multimetal metallocene compounds obtained from embodiments of the present invention can be used as catalysts for olefin polymerization.

The method of preparing the copolymer of ethylene, alpha-olefin and diolefin using the transition metal catalyst composition of the present invention is not particularly limited, but may be carried out, for example, in the presence of an appropriate organic solvent, A multimetal metallocene compound catalyst, a cocatalyst, and ethylene and alpha-olefin and diolefin comonomers in a batch reaction or continuous reaction in solution. When two or more of the reactors are used in series or in parallel, the reactants may be used in the form of a mixture of physically and chemically mixed copolymers having different molecular weights and densities depending on the reaction fraction. Coalescence may be produced.

Preferred organic solvents that may be used in the above process are C3-C20 hydrocarbons. Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, isooctane, nonane, decane, dodecane, cyclohexane, methylcyclohexane , Benzene, toluene, xylene, etc. In some cases, a mixture of two or more of the organic solvents may be used.

The olefins used in the polymerization of olefins according to the present invention include, for example, C2-20 alpha-olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene; C4-20 diolefins such as 1,3-butadiene, 1,4-pentadiene and 2-methyl-1,3-butadiene; Cycloolefins or cyclo-olefins of C3 to 20 such as cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene, norbornene, methyl-2-norbornene, and ethylidene; Styrene or styrene substituted with C1-10 alkyl, C1-10 alkoxy, halogen, amine, silyl, halogenated alkyl or the like. In the present invention, the above olefins can be homopolymerized or two or more olefins can be copolymerized.

In the polymerization of olefins, the polymerization temperature and pressure are not particularly limited, but it is -50 to 200 占 폚, preferably 0 to 150 占 폚. The polymerization pressure is 0.5 to 5,000 atm, preferably 1 to 500 atm Preferably from 1 to 50 atm.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

< Multi metal Metallocene  Synthesis of Compound &gt;

All synthesis reactions proceeded in an inert atmosphere, such as nitrogen, using Schlenk Technique technology and a glove box.

Tetrahydrofuran (THF), toluene, n-hexane, diethyl ether, dimethyl ether, etc. were used as a moisture absorber.

[Example 1]

{4- [1- (N-t-butylamidodimethylsilyl) -2,3,4- Trimethylcyclopentadienyl )] Phenyl ether} {Titanium dichloride} ₂  of  synthesis

(1) 4- (2,3,4- Trimethylcyclopentadienyl ) Synthesis of phenyl ether

9.84 g (30 mmol) of 4-bromophenyl ether was dissolved in 100 mL of diethyl ether, and 24 mL of 2 equivalents of butyllithium was added at -78 째 C.

The temperature was slowly raised to room temperature and then stirred for another two hours. The precipitate was allowed to settle and the supernatant was removed, and 30 mL of tetrahydrofuran was added thereto. Again, the above reaction solution was cooled to -78 ° C, and a solution obtained by dissolving 8.9 g of 2,3,4-trimethyl-2-cyclopent-2-enone in 20 mL of tetrahydrofuran was added slowly at the same temperature . After slowly raising the temperature to room temperature and stirring for 6 hours or more, 50 mL of an aqueous saturated ammonium chloride (NH ₄ Cl) solution was added.

The resulting organic and aqueous layers were separated and the aqueous layer was extracted twice with 50 mL portions of diethyl ether and combined with the organic layer. The combined organic solution layer was dried over anhydrous magnesium sulfate (MgSO ₄ ) to remove moisture, and the resulting solution was dried under vacuum to obtain the desired liquid product.

After dissolving in 30 mL of dichloromethane at room temperature, 0.1 g of a catalytic amount of p-toluenesulfonic acid hydrate was added in a solid state. After stirring for about one hour, it was dried in vacuo and recrystallized with ethanol to obtain a pale yellow solid.

^{1 H-NMR (400.13 MHz,} CDCl3, ppm): δ 7.30 (d, 4H, C6 H4), 7.01 (d, 4H, C6 H4), 3.18 (s, 4H, C5Me3 H2), 2.07 (s, 6H, C5 Me 3H2), 2.00 (s , 6H, C5 Me3 H2), 1.88 (s, 6H, C5 Me3 H2)

( 2) 4 - [1- (N-t- Butylaminodimethylsilyl ) -2,3,4- Trimethyl - Cyclopentadienyl )] Synthesis of phenyl ether

3.82 g of 4- (2,3,4-trimethylcyclopentadienyl) phenyl ether obtained in the above step (1) was dissolved in 30 mL of tetrahydrofuran, and then 8 mL of 2 equivalents of n-butyllithium was added thereto at -78 ° C. Respectively. After the temperature was raised to room temperature, the mixture was stirred for 2 hours or more, and 4.5 mL of Me ₂ SiCl ₂ was added thereto at -78 ° C. After stirring for about 4 hours at room temperature, all of the solvent was removed, and the residue was extracted with n-hexane to remove the remaining solid. After removing all of the hexane, it was dried in a vacuum for 4 hours or more. After dissolving in tetrahydrofuran again, 6.5 mL of t-butylamine was added at -78 ° C. The mixture was heated to room temperature and stirred for 6 hours or more. After drying all of the solvent, the solution was extracted with n-hexane to remove the remaining solid, and then n-hexane was removed in vacuo to obtain a yellow liquid substance.

^{1 H-NMR (400.13 MHz,} CDCl3, ppm): δ 7.33 (d, 4H, C6 H4), 7.03 (d, 4H, C6 H4), 3.49 (s, 2H, C5Me3 H), 2.08 (s, 6H, C5 Me3 H), 2.05 (s , 6H, C5 Me3 H), 1.90 (s, 6H, C5 Me3 H), 0.94 (s, 18H, NHC Me3), 0.32 (s, 2H, N H CMe3), -0.13 (s, 6H, Me2Si ), -0.30 (s, 6H, Me2Si ).

(3) {4- [1- (N-t- Butylamido dimethylsilyl ) -2,3,4- Trimethylcyclopentadienyl )] Phenyl ether} {Titanium dichloride} ₂  of  synthesis

3.21 g of 4- [1- (Nt-butylaminodimethylsilyl) -2,3,4-trimethyl-cyclopentadienyl)] phenyl ether obtained in the above (2) was dissolved in 30 mL of tetrahydrofuran, 4 equivalents of n-butyllithium were added at 78 占 폚. After the temperature was raised to room temperature, the mixture was stirred for 4 hours or more, and 3.71 g of TiCl ₃ (thf) ₃ dissolved in 20 mL of tetrahydrofuran was added slowly at -78 ° C. After stirring at room temperature for 6 hours or more, 2 equivalents of AgCl ₂ were added in solid phase to the reaction solution at room temperature. After stirring for about 2 hours, the solvent was vacuum dried. The obtained solid was dissolved in toluene, the solution phase was separated from the remaining solid, and the solvent was dried to obtain a pale brown solid compound.

^{1 H-NMR (400.13 MHz,} CDCl3, ppm): δ 7.20 (d, 4H, C6 H4), 6.98 (d, 4H, C6 H4), 2.31 (s, 6H, C5 Me3 H), 2.24 (s, 6H , C5 Me3 H), 2.19 ( s, 6H, C5 Me3 H), 1.41 (s, 18H, NHC Me3), 0.65 (s, 6H, Me2 Si), -0.10 (s, 6H, Me2 Si).

[Example 2]

{4- [1- (N-t-butylamidodimethylsilyl) -3,4-dimethyl- Cyclopentadienyl )] Phenyl ether} {titanium Dichloride } ₂  of  synthesis

(1) 4- (3,4- Dimethylcyclopentadienyl ) Synthesis of phenyl ether

9.84 g (30 mmol) of 4-bromophenyl ether was dissolved in 100 mL of diethyl ether, and 24 mL of 2 equivalents of butyllithium was added at -78 째 C.

The temperature was slowly raised to room temperature and then stirred for another two hours. The precipitate was allowed to settle and the supernatant was removed, and 30 mL of tetrahydrofuran was added thereto. The reaction solution was cooled to -78 ° C, and a solution of 8.5 g of 3,4-dimethyl-2-cyclopent-2-enone in 20 mL of tetrahydrofuran was slowly added thereto at the same temperature. After slowly raising the temperature to room temperature and stirring for 6 hours or more, 50 mL of an aqueous saturated ammonium chloride (NH ₄ Cl) solution was added.

The resulting organic and aqueous layers were separated and the aqueous layer was extracted twice with 50 mL portions of diethyl ether and combined with the organic layer. The combined organic solution layer was dried over anhydrous magnesium sulfate (MgSO ₄ ) to remove water and the solid was removed, and the obtained solution was dried under vacuum to obtain the desired liquid product.

After dissolving in 30 mL of dichloromethane at room temperature, 0.1 g of a catalytic amount of p-toluenesulfonic acid hydrate was added in a solid state. After stirring for about one hour, it was vacuum dried and then recrystallized with ethanol to obtain a pale yellow solid.

^{1 H-NMR (400.13 MHz,} CDCl3, ppm): δ 7.41 (d, 4H, C6 H4), 6.95 (d, 4H, C6 H4), 6.59 (. S 2H, C5Me2 H3), 3.27 (s, 4H, C5 Me2 H3 ), 1.99 (s, 6H, C5 Me2 H3), 1.91 (s, 6H, C5Me3H2)

( 2) 4 - [1- (N-t- Butylaminodimethylsilyl ) -3,4-dimethyl- Cyclopentadienyl )] Synthesis of phenyl ether

3.54 g of 4- (3,4-dimethylcyclopentadienyl) phenyl ether obtained in the above (1) was dissolved in 30 mL of tetrahydrofuran, and then 8 mL of 2 equivalents of n-butyllithium was added at -78 ° C. After warming to room temperature, stir for 2 hours or more, add 4.5 mL of Me ₂ SiCl ₂ at -78 ° C. After stirring for about 4 hours at room temperature, all of the solvent was removed, and the residue was extracted with n-hexane to remove the remaining solid. After removing all of the hexane, it was dried in a vacuum for 4 hours or more. After dissolving in tetrahydrofuran again, 6.5 mL of t-butylamine was added at -78 ° C. The mixture was heated to room temperature and stirred for 6 hours or more. After drying all of the solvent, the mixture was extracted with n-hexane to remove the remaining solid, and then n-hexane was removed in vacuo to obtain a yellow liquid substance.

^{1 H-NMR (400.13 MHz,} CDCl3, ppm): δ 7.30 (d, 4H, C6H4), 6.95 (d, 4H, C6H4), 6.50 (s, 2H, C5Me2H2), 3.70 (s, 2H, C5Me2H2), (S, 6H, C5Me2H2), 1.94 (s, 6H, C5Me2H2), 1.08 (s, 18H, NHCMe3), 0.51 (s, 2H, NHCMe3), 0.13 6H, Me2Si)

(3) {4- [1- (N-t- Butylamido dimethylsilyl ) -3,4-dimethyl- Cyclopentadienyl )] Phenyl ether} {titanium Dichloride } ₂ Synthesis of

4- [1- (Nt-butylaminodimethylsilyl) -3,4-dimethyl-cyclopentadienyl)] phenyl ether obtained from the above-mentioned (2) 3.06 g was dissolved in 30 mL of tetrahydrofuran, and then 4 equivalents of n-butyllithium was added at -78 deg. After the temperature was raised to room temperature, the mixture was stirred for 4 hours or more, and 3.71 g of TiCl ₃ (thf) ₃ dissolved in 20 mL of tetrahydrofuran was added slowly at -78 ° C. After stirring at room temperature for 6 hours or more, 2 equivalents of AgCl were added to the reaction solution at room temperature in a solid phase. After stirring for about 2 hours, the solvent was vacuum dried. The obtained solid was dissolved in toluene, the solution phase was separated from the remaining solid, and the solvent was dried to obtain a pale brown solid compound.

^{1 H-NMR (400.13 MHz,} CDCl3, ppm): δ 7.60 (d, 4H, C6H4), 6.95 (d, 4H, C6H4), 6.76 (s, 2H, C5Me2H), 2.39 (s, 6H, C5Me2H), 6H, C5Me2H), 1.40 (s, 18H, NHCMe3), 0.72 (s, 6H, Me2Si), 0.11 (s, 6H, Me2Si).

&Lt; Preparation of Polymer &

In order to confirm the availability of the multimetal metallocene compounds obtained from Examples 1 and 2, an olefin polymer was prepared.

The obtained polymer may exhibit various molecular weights depending on the production conditions. Molecular weight and molecular weight distribution were measured by gel chromatography, which consisted of three columns. The solvent used herein was 1,2,4-trichlorobenzene, and the measurement temperature was 120 占 폚. In order to evaluate the composition of the copolymer, a film specimen was prepared with a press specimen maker, and the ratio of ethylene to alpha-olefin and the content of diene were quantified using an infrared spectroscope.

[Example 3]

1 L of n-hexane was added to a stainless steel reactor having a capacity of 2 L, and then 500 mmol of modified triisobutyl aluminum (Sigma Aldrich, TIBA) was added to the reactor. Then, according to the initial composition, the weight ratio of propylene / ethylene was 1.0, and the reactor pressure was 5 kg / cm ² And then the temperature of the reactor was heated to 60 占 폚. The reaction was initiated by the sequential addition of 5 mmol of the compound of Example 1 and 10 mmol of triphenyllium tetrakispentafluorophenyl borate (99%, Boulder Scientific). When the reaction proceeded, ethylene and propylene were continuously fed according to the initial composition so that the pressure in the reactor was maintained at 5 kg / cm &lt; ^{2 &} gt ;. As soon as the reaction started, the reaction temperature was raised to 20 ° C or more due to the exothermic reaction. After 20 minutes, the polymerized solution was drained to terminate the reaction. The polymerized solution was precipitated in a sufficient acetone solvent and recovered. The polymer solution was vacuum dried at 60 ° C for 12 hours, and the polymerization activity was 18.9 kg / g.cat. The polymer had a weight average molecular weight of 520,000 (g / mol) and a distribution of 3.3. And the ethylene content of the polymer via infrared spectroscopy was 57% by weight.

[Example 4]

Except that 18 g of 5-ethylidene-2-norbornene (Sigma Aldrich), a polyene monomer, was added. As a result, the polymerization activity was 16.5 kg / g.cat. The polymer had a weight average molecular weight of 370,000 (g / mol) and a distribution of 2.5. The polymer had an ethylene content of 59% by weight and an ENB content of 4.8% by weight by infrared spectroscopy.

[Example 5]

The polymerization activity was measured in the same manner as in Example 4 except that the polymerization initiation temperature was 80 ° C. As a result, the polymerization activity was 13.2 kg / g.cat. The polymer had a weight average molecular weight of 310,000 (g / mol) and a distribution of 2.6. And the polymer had an ethylene content of 62% by weight and an ENB content of 4.2% by weight by infrared spectroscopy.

[Example 6]

The polymerization activity was 7.1 kg / g.cat as a result of carrying out the same procedure as in Example 4 except that the polymerization initiation temperature was 100 ° C. The polymer had a weight average molecular weight of 250,000 (g / mol) and a distribution of 2.7. And the ethylene content of the polymer through infrared spectroscopy was 65 wt%, and the content of ENB was 4.3 wt%.

[Example 7]

The polymerization activity was 17.0 kg / g.cat as a result of the same procedure as in Example 4 except that the transition metal catalyst compound of Example 2 was used instead of the transition metal catalyst compound of Example 1 as the polymerization main catalyst. The polymer had a weight average molecular weight of 550,000 (g / mol) and a distribution of 3.5, and the polymer had an ethylene content of 60% by weight and an ENB content of 6.5% by weight by infrared spectroscopy.

[Example 8]

The polymerization activity was 15.1 kg / g.cat as a result of carrying out the same procedure as in Example 7 except that the polymerization initiation temperature was 80 ° C. The polymer had a weight average molecular weight of 320,000 (g / mol) and a distribution of 2.8. The polymer had an ethylene content of 60% by weight and an ENB content of 6.3% by weight by infrared spectroscopy.

[Example 9]

The polymerization activity was 12.8 kg / g.cat as a result of carrying out the same procedure as in Example 7 except that the polymerization initiation temperature was 100 ° C. The weight average molecular weight of the polymer was 120,000 (g / mol) and the distribution was 3.0. The polymer had an ethylene content of 58% and an ENB content of 6.9% by infrared spectroscopy.

Claims (7)

A process for producing a copolymer comprising ethylene, propylene and a diene monomer using a multimetal metallocene compound represented by the following general formulas (1) to (2).
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
M ₁ and M ₂ are the same or different and are a transition metal or a lanthanide metal of the group 3 to 10 having an oxidation number of +2 to +4,
A is a heteroatom other than carbon, selected from oxygen, nitrogen, sulfur and phosphorus,
Ar ₁ And Ar ₂ are independently (C6-C30) arylene groups,
R ₁ to R ₆ are, independently of each other, selected from the group consisting of hydrocarbyl, hydrocarbylsilyl, halohydrocarbyl, hydrocarbyloxyhydrocarbyl, dihydrocarbylaminohydrocarbyl, dihydrocarbyl a A hydrocarbyloxy group which may be covalently bonded to each other to form one or two or more conjugated or non-conjugated rings,
Z ₁ and Z ₂ are independently of each other a functional group having two bonding sites,
Y ₁ and Y ₂ are independently a functional group having two bonding sites, Y ₁ is bonded to M ₁ and Z ₁ , Y ₂ is bonded to M ₂ and Z ₂ ,
Xn is an anion or a double anion ligand. The method according to claim 1,
Propylene and a diene monomer, using a multimetal metallocene compound wherein M ₁ and M ₂ are selected from Ti, Zr and Hf. The method according to claim 1,
Z ₁ and Z ₂ each independently is ^{_{-SiR * 2 -, -CR * 2}} -, -GeR * 2 - or -BR ^* - (wherein, R ^* is independently hydrogen, or selected hydrocarbyl, hydrocarbyl-oxy, Silyl, halogenated alkyl or halogenated aryl having 1 to 20 atoms other than hydrogen may be connected to each other to form a cyclic structure), a copolymer of ethylene, propylene and a diene monomer containing a metallocene metallocene compound Gt; The method according to claim 1,
Y ₁ and Y ₂ are each independently -NR ^* -, -PR ^* -, -O- or -S-, wherein R ^* is independently hydrogen or a selected hydrocarbyl, hydrocarbyloxy, silyl, halogenated Wherein the alkyl or halogenated aryl has 1 to 20 atoms other than hydrogen.) A process for producing a copolymer comprising ethylene, propylene and a diene monomer using a metallometallic metallocene compound. The method according to claim 1,
X _n independently from each other are selected from the group consisting of halogen atoms, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 30) ar (C 1 -C 20) (C6-C30) arylsiloxy, (C1-C20) alkylamino or (C6-C30) arylamino group and n has a number of 0 to 4 depending on the oxidation number of M ₁ and M ₂ A process for producing a copolymer comprising ethylene, propylene and a diene monomer by using a metallocene metallocene compound. The method according to claim 1,
Wherein the multimetal metallocene compound is selected from compounds represented by the following structural formulas, wherein the multimetal metallocene compound is selected from compounds represented by the following structural formulas.

The method according to claim 1,
Wherein the multimetal metallocene compound is {4- [1- (Nt-butylamidodimethylsilyl) -2,3,4-trimethylcyclopentadienyl]] phenyl ether} {titanium dichloride} ₂ or {4- a - [1- (Nt- butylamido dimethylsilyl) -3,4-dimethyl-cyclopentadienyl)] titanium dichloride ether} {} ₂ is ethylene, propylene and a diene monomer with a metallocene compound of a metal-metal &Lt; / RTI &gt;