KR101844152B1 - Process for ethylene/alpha olefin/diene terpolymer using new transition metal compound - Google Patents

Abstract

The addition of an olefin type diene such as 1,5-hexadiene to an existing ethylene /? - olefin copolymer such as ethylene / 1-octene leads to the formation of some crosslinked material at the same time as the polymerization and the production of a polymer having improved tensile elongation and tensile strength / RTI > The present invention provides a process for producing an ethylene- alpha -olefin-diene terpolymer comprising polymerizing a monomer containing ethylene, alpha -olefin and diene under a catalyst containing a transition metal compound represented by the following formula (1).
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a process for producing an ethylene-alpha-olefin-diene terpolymer using a novel transition metal,

TECHNICAL FIELD The present invention relates to a process for producing an ethylene- alpha -olefin-diene terpolymer, and more particularly, to a process for producing an ethylene- alpha -olefin-diene terpolymer using a metallocene catalyst.

Most of the tri-monomer polymers are concerned with ethylene, alpha-olefins, cyclic olefins or aromatic monomers such as divinylbenzene (DVB), and the terpolymer of ethylene and high- α -olefin and diene olefin monomers Research on the subject is extremely rare.

In general, the tri-monomer polymerization of ethylene / alpha -olefin and diene has the advantages of a terpolymer having a narrow molecular weight distribution while dissolving in a divinylbenzene bond frequently used as a diene. However, the use of an aromatic monomer The environment is not good, and it is necessary to quickly produce the polymerization inhibitor after removing the polymerization inhibitor, which is essential for the storage of the divinylbenzene, so that the self-polymerization can be prevented and the piping phenomenon caused by the self-polymerization can be prevented.

These difficult-to-handle monomers are expensive to produce in industrial production, thus raising the cost of the product. Also, in the case of the terpolymer containing divinylbenzene, due to the specific odor due to divinylbenzene, the quality of the final product and the convenience of the consumer may become a problem in the future.

[Prior Patent Literature]

U.S. Patent No. 6,265,493 (July 24, 2001)

- U.S. Patent No. 5,696,213 (Dec. 9, 1997)

The present invention relates to a polymer having an improved olefin-type diene such as 1,5-hexadiene added to an ethylene / alpha -olefin copolymer such as ethylene / 1-octene to improve the tensile elongation and tensile strength Which is capable of being produced.

According to an aspect of the present invention, there is provided a process for producing ethylene-α-olefin-diene tri A method for producing a polymer is provided.

[Chemical Formula 1]

M is 2 and n is 0 and M is 0 and n is 1 when M is a divalent transition metal of Group 4 in the periodic table; is M and η ⁵ - is a cyclopentadienyl ring which can be combined, wherein the cyclopentadienyl ring (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, tri (C1- (C6-C20) arylsilyl, (C6-C20) arylsilyl, (C1-C20) alkyldi It can be further substituted with one or more selected from the group consisting of alkenyl and; D is SiR ³ R ⁴ or (C2-C20) alkenylene; R ³ and R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) or cycloalkyl, or (C6-C20) aryl, wherein R ³ and R ⁴ are (C4-C7) are connected by an alkylene to form a ring, and; R ¹ is (C1-C20) alkyl ; Ar is (C6-C20) aryl; R ² is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6- C20) aryl; wherein Ar and R ² are (C1-C7) alkylene, (C2-C7) alkenylene or a (C4-C7) are connected to the alkane diethoxy alkenylene may form a fused ring; X ¹ is a halogen , (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) ^{aryloxy, -OSiR a R b R c,} -SR d, -NR ^e R ^f or R ^h and -PR ^g; R ^a to R ^h are each independently (C1-C20) alkyl, (C6-C20) aryl or (C3-C20) cycloalkyl; X ² is a neutral conjugated or non-conjugated (C4-C20) diene, and; wherein the R ¹ alkyl, an Ar aryl, R ^2, R ³ and R ⁴ for alkyl, cycloalkyl, aryl are independently from each other are selected from halogen, (C1-C20) alkyl, Which may be further substituted with one or more substituents selected from the group consisting of halo (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 20) aryl, (C 1 -C 20) alkoxy and have.)

Further, the amount of the catalyst added is 10 ^-8 to 1 mol / L based on the concentration of the central metal (M) in the transition metal compound per unit volume (L) of the monomer.

The α-olefin monomer is at least one member selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, 1-decene and 1-dodecene, and the diene monomer is a C4- Wherein the monomer is at least one member selected from the group consisting of an aliphatic monomer, a C5-C20 aliphatic non-conjugated diene monomer, a C5-C20 cyclic non-conjugated diene monomer, and a C6-C20 aromatic non-conjugated diene monomer. to provide.

And the ethylene -? - olefin-diene terpolymer has a weight average molecular weight (Mw) of 10,000 to 1,000,000.

And the ethylene -? - olefin-diene terpolymer has a molecular weight distribution (Mw / Mn) of 1 to 15.

And the ethylene -? - olefin-diene terpolymer has a density of 0.850 to 0.920 g / ml.

The process for preparing an ethylene -? - olefin-diene terpolymer according to the present invention makes it possible to prepare a copolymer having a tensile elongation and a tensile strength which are improved compared to conventional ethylene / 1-octene copolymers.

Further, addition of a diene such as 1,5-hexadiene has the effect of obtaining a polymer having improved tensile properties as a result of the formation of some crosslinked materials at the same time as polymerization.

Further, by adding a polymer to be produced to the polypropylene resin composition for a film, the stretching force of the film due to the improvement in tensile elongation can be increased.

Hereinafter, preferred embodiments of the present invention will be described in detail. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, when an element is referred to as "including " an element, it means that it can include other elements, not excluding other elements, unless specifically stated otherwise.

The process for producing an ethylene-? -Olefin-diene terpolymer according to the present invention comprises polymerizing a monomer containing ethylene,? -Olefin and a diene under a catalyst containing a transition metal compound represented by the following formula (1).

[Chemical Formula 1]

M is 2 and n is 0 when M is a tetravalent transition metal of Group 4 on the periodic table and m is 0 and n is 1 when M is a divalent transition metal of Group 4 on the periodic table; Cp is a cyclopentadienyl ring which may be bound to M by η ⁵ - and the cyclopentadienyl ring is optionally substituted with one or more substituents selected from the group consisting of (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl, (C 6 -C 20) (C6-C20) alkylsilyl, tri (C6-C20) arylsilyl, (C1-C20) alkyldi ≪ / RTI >alkenyl; D is SiR ³ R ⁴ or (C2-C20) alkenylene; R ³ and R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6-C20) aryl, wherein R ³ and R ⁴ are connected to the (C4-C7) alkylene To form a ring; R < ¹ > is (C1-C20) alkyl; Ar is (C6-C20) aryl; R ² is hydrogen, (C 1 -C 20) alkyl, (C 3 -C 20) cycloalkyl or (C 6 -C 20) aryl; Ar and R ² may be linked by (C 1 -C 7) alkylene, (C ² -C 7) alkenylene or (C 4 -C 7) alkane dienylene to form a fused ring; X ¹ is halogen, (C1-C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) aryloxy, -OSiR ^a R ^b R ^c, -SR ^d , -NR ^e R ^f or -PR ^g R ^h ; R ^a to R ^h are, independently of each other, (C 1 -C 20) alkyl, (C 6 -C 20) aryl or (C 3 -C 20) cycloalkyl; X ² is a neutral, conjugated or nonconjugated (C4-C20) diene; Alkyl, Ar of the R ¹ aryl, R ^2, R ³ and the R ⁴ alkyl, cycloalkyl, aryl are independently from each other are selected from halogen, (C1-C20) alkyl, halo (C1-C20) alkyl, (C3-C20 ) Cycloalkyl, (C6-C20) aryl, (C1-C20) alkoxy and (C6-C20) aryloxy.

The term " alkyl " as used herein refers to a monovalent straight or branched saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms. Examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Butyl, pentyl, hexyl, octyl, dodecyl, and the like.

The term " cycloalkyl " as used in the present invention means a monovalent alicyclic alkyl radical consisting of one ring, examples of which include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, But are not limited to, cyclononyl, cyclodecyl, and the like.

The term " alkenyl " as used herein also refers to straight or branched chain hydrocarbon radicals containing one or more carbon-carbon double bonds, including ethenyl, propenyl, butenyl, pentenyl and the like, But is not limited to.

The term " aryl ", as defined in the present invention, is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, including a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyreneyl, perylenyle, klycenyl, naphthacenyl, fluoranthenyl and the like.

The term " alkoxy " as used in the present invention means an -O-alkyl radical where 'alkyl' is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

The term " halogen " as used in the present invention means a fluorine, chlorine, bromine or iodine atom.

In the present invention, the transition metal compound is a cyclopentadiene derivative ligand connected with a bridge group of silicon or alkenylene and an anisole derivative ligand in which the aryl is substituted at the 4-position, And has an ansa-metallocene structure.

Thus, the transition metal compound has an aldehyde derivative ligand in which aryl is substituted at the 4-position, and has superior catalytic activity and copolymerization as compared with a transition metal compound having an aryl group-unsubstituted ligand at the 4-position of indene .

In one embodiment of the present invention, the transition metal compound of the formula (1) can be preferably represented by the following formula (2) or (3).

(2)

(3)

In the general formulas (2) and (3), M ¹ is a tetravalent Group 4 transition metal, M ² is a divalent Group 4 transition metal and Cp, Ar, R ¹ to R ⁴ , X ¹ and X ² are as defined in Chemical Formula same.

In one embodiment of the present invention, m is 2 and n is 0 when M is tetravalent titanium, zirconium or hafnium, m is 0 when M is divalent titanium, zirconium or hafnium, and n is 1; Cp is a cyclopentadienyl ring in which (C1-C20) alkyl is substituted or unsubstituted; R ¹ is (C ¹ -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl or halo (C 1 -C 20) alkyl; Ar is (C6-C20) aryl; R ² is hydrogen or (C 6 -C 20) aryl; Ar and R ² may be linked to form a fused ring with (C 1 -C 7) alkylene, (C ² -C 7) alkenylene or (C 4 -C 7) alkane dienylene, and the aryl of Ar and R ² may be halogen (C6-C60) aryloxy, (C6-C60) aryloxy, (C6-C60) aryloxy, Lt; / RTI > may be further substituted with a substituent; R ³ and R ⁴ are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, halo (C 1 -C 20) C20) aryl, R < ³ > and R < ⁴ > may be linked by (C4-C7) alkylene to form a ring; X ¹ is halogen, (C ¹ -C 20) alkyl, (C 1 -C 20) alkoxy or di (C 1 -C 20) alkylamino; X ² can be a neutral conjugated 1,3- (C4-C20) diene.

In one embodiment of the present invention, in Formulas 2 and 3, M ¹ is tetravalent titanium, zirconium or hafnium; M ² is divalent titanium, zirconium or hafnium; Cp is a cyclopentadienyl ring in which (C1-C20) alkyl is substituted or unsubstituted; R ¹ is (C ¹ -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl or halo (C 1 -C 20) alkyl; Ar is (C6-C20) aryl; R ² is hydrogen or (C 6 -C 20) aryl; Ar and R ² may be linked to form a fused ring with (C 1 -C 7) alkylene, (C ² -C 7) alkenylene or (C 4 -C 7) alkane dienylene, and the aryl of Ar and R ² may be halogen (C6-C60) aryloxy, (C6-C60) aryloxy, (C6-C60) aryloxy, Lt; / RTI > may be further substituted with a substituent; R ³ and R ⁴ are independently selected from the group consisting of (C 1 -C 20) alkyl, (C 6 -C 20) aryl (C 1 -C 20) alkyl, halo (C 1 -C 20) C20) aryl, R < ³ > and R < ⁴ > may be linked by (C4-C7) alkylene to form a ring; X ¹ is halogen, (C ¹ -C 20) alkyl, (C 1 -C 20) alkoxy or di (C 1 -C 20) alkylamino; X ² can be a neutral conjugated 1,3- (C4-C20) diene.

In one embodiment of the present invention, the Cp is cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl or butylcyclopentadienyl; R ¹ is methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl or trifluoromethyl; Ar is phenyl, naphthyl, biphenyl or anthryl; R ² is hydrogen, phenyl, naphthyl, biphenyl or anthryl; The phenyl, naphthyl, biphenyl or anthryl of Ar and R ² is optionally substituted with one or more substituents selected from the group consisting of fluoro, chloro, iodo, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, trifluoromethyl, cyclopropyl, Which may be further substituted with one or more substituents selected from the group consisting of alkyl, cyclohexyl, phenyl, naphthyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and phenoxy; Wherein Ar and R ² may be connected to each other by methylene, ethenylene or 1,3-butane dienylene to form a fused ring, and R ³ and R ⁴ may be the same or different and are each a methyl, ethyl, propyl, butyl, pentyl, hexyl, Fluoromethyl, phenyl, naphthyl, biphenyl, anthryl or tolyl, and R ³ and R ⁴ may be linked together with a butylene or pentylene to form a ring; X ¹ is selected from the group consisting of fluoro, chloro, iodo, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, Amino, dipropylamino, dibutylamino, butylpropylamino, dihexylamino, dioctylamino or methylethylamino; X ² can be 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene or 1,3-octadiene.

In one embodiment of the present invention, the transition metal compound may be selected from compounds having the following structures, but is not limited thereto.

In the above structure, Cp is cyclopentadienyl, methylcyclopentadienyl, dimethylcyclopentadienyl, diisopropylcyclopentadienyl, trimethylcyclopentadienyl or tetramethylcyclopentadienyl; M1 is tetravalent titanium, zirconium or hafnium; X1 is chloro, fluoro, bromo, methyl, ethyl, propyl, butyl, pentyl, methoxy, ethoxy, propoxy, butoxy or dimethylamino.

On the other hand, the transition metal compound represented by the general formula (1) can be used as an active catalyst component used in the ethylene-alpha-olefin-diene terpolymerization by extracting a ligand in the transition metal compound and cationizing the center metal, The compounds represented by the following formulas (4) to (6) which can act as anions act together as a cocatalyst.

[Chemical Formula 4]

- [Al (R17) -O] n-

In the general formula (4), R 17 is the same or different and each independently represents a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen; n is an integer of 2 or more.

[Chemical Formula 5]

A (R18) 3

In Formula 5, A is aluminum or boron; R18 are the same or different and each independently represent a hydrocarbyl radical having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen radical or a halogen.

[Chemical Formula 6]

^{[LH] + [Z (B} ) 4] - or ^{[L] + [Z (B} ) 4] -

In Formula 6, L is a neutral or cationic Lewis acid; H is a hydrogen atom;

Z is a Group 13 element; B are each independently an aryl or alkyl radical having from 6 to 20 carbon atoms in which at least one hydrogen atom is replaced by halogen, hydrocarbyl having from 1 to 20 carbon atoms, alkoxy, or phenoxy radical.

In order to allow the above-mentioned co-catalyst compound to exhibit a more excellent activation effect, the compound represented by the general formula (4) is not particularly limited as long as it is alkylaluminoxane, but preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, Aluminoxane, and the like. Particularly preferred compounds are methylaluminoxane.

The alkyl metal compound represented by Formula 5 is not particularly limited, but preferable examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, t-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p- Particularly preferred compounds are selected from among trimethylaluminum, triethylaluminum and triisobutylaluminum. Preferred examples of the compound include trimethylaluminum, trimethylaluminum, trimethylaluminum, trimethylaluminum, triethylaluminum, have.

Furthermore, in the co-catalyst compound represented by the formula (6), the [LH] ⁺ is dimethylanilinium cation-dimethyl, wherein [Z (A) 4] ^- is [B (C6F5) 4] ^- and it is preferably, the [ L] ⁺ is [(C6H5) 3C] ⁺ , and [Z (A) 4] ^- is [B (C6F5) 4] ^- . Herein, the co-catalyst compound represented by Formula 4 is not particularly limited, but examples thereof include triethylammonium tetraphenyl borate, tributylammonium tetraphenyl borate, trimethylammonium tetraphenyl borate, tripropylammonium tetraphenyl (O, p-dimethylphenyl) borate, triethylammoniumtetra (p-tolyl) borate, tripropylammoniumtetra (p- tolyl) borate, trimethylammoniumtetra Phenyl) borate, tributylammoniumtetra (ptrifluoromethylphenyl) borate, trimethylammoniumtetra (p-trifluoromethylphenyl) borate, tributylammonium tetrapentafluorophenylborate, N, Amylidium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrapentafluorophenyl Borate, diethylammonium tetrapentafluorophenylborate, triphenylphosphonium tetraphenylborate, trimethylphosphonium tetraphenylborate, triphenylcarboniumtetra (p-trivoloromethylphenyl) borate, triphenylcarbonium Tetrapentafluorophenyl borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, and the like.

The addition amount of the above-mentioned co-catalyst compound can be determined in consideration of the addition amount of the transition metal compound represented by the above-mentioned formula (1) and the amount necessary for sufficiently activating the above promoter compound. The content of the co-catalyst compound may be 1: 1 to 100,000, based on the molar ratio of the metal contained in the co-catalyst compound to 1 mole of the transition metal contained in the transition metal compound represented by the formula (1) 1: 1 to 10,000, more preferably 1: 1 to 5,000.

More specifically, the compound represented by Formula 4 is preferably used in a molar ratio of 1: 10 to 5,000, more preferably 1: 50 to 1,000, and most preferably 1: 100 to 1,000 molar ratio. When the molar ratio of the compound represented by the formula (2) to the transition metal compound represented by the formula (1) is less than 1:10, the amount of the aluminoxane is so small that the activation of the metal compound may not proceed completely, The excess aluminoxane acts as a catalyst poison to prevent the polymer chain from growing well.

When A is boron in the promoter compound represented by Formula 5, the transition metal compound represented by Formula 1 is used in a ratio of 1: 1 to 100, preferably 1: 1 to 10, more preferably 1: May be carried at a molar ratio of 1 to 3. In the co-catalyst compound represented by Formula 3, when A is aluminum, the amount of water may vary depending on the amount of water in the polymerization system. However, the amount of the transition metal compound represented by Formula 1 is preferably 1: 1 to 1000, : 1 to 500, and more preferably 1: 1 to 100.

The promotor compound represented by Formula 6 is supported on the transition metal compound represented by Formula 1 at a molar ratio of 1: 1 to 100, preferably 1: 1 to 10, more preferably 1: 1 to 4, . When the ratio of the promoter compound represented by Chemical Formula 4 is less than 1: 1, the amount of the activator is relatively small and activation of the metal compound is not completely performed, : 100, the activation of the metal compound is completely performed, but the unit cost of the catalyst composition may not be economical due to the excess activator remaining, or the purity of the produced polymer may be lowered.

Meanwhile, the catalyst according to the present invention may further include a carrier in the compound represented by Formula 1 and the co-catalyst compound.

As the carrier, inorganic or organic carrier used in the production of the catalyst in the technical field of the present invention may be used without limitation, for example, SiO ₂ , Al ₂ O ₃ , MgO, MgCl ₂ , CaCl ₂ , ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -CrO ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, bauxite, zeolite, starch, cyclodextrine, synthetic polymer and the like can be used. Preferably, the carrier comprises a hydroxy group on the surface, and may be at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia.

The method of supporting the transition metal compound and the promoter compound on the carrier includes a method of directly supporting the transition metal compound on a dehydrated carrier, a method of pretreating the carrier with the promoter compound, A method in which the transition metal compound is supported on the support, followed by post treatment with a promoter compound, a method in which the transition metal compound is reacted with a cocatalyst compound, and then a carrier is added and reacted.

The solvent usable in the above carrying method may be an aromatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixture thereof. The aliphatic hydrocarbon solvent may include, but is not limited to, pentane, hexane, heptane, octane, nonane, decane, undecane, Dodecane and the like. Examples of the aromatic hydrocarbon solvents include, but are not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, and toluene. Examples of the halogenated aliphatic hydrocarbon solvent include, but are not limited to, dichloromethane, trichloromethane, dichloroethane, and trichloroethane

The step of carrying the transition metal compound and the co-catalyst compound on the carrier is carried out at a temperature of -70 to 200 ° C, preferably -50 to 150 ° C, more preferably 0 to 100 ° C, .

In the present invention, the polymerization of ethylene, alpha -olefin and diene can be carried out in a slurry phase, a solution phase, a gas phase or a bulk phase.

When the polymerization reaction is carried out in a liquid phase or a slurry, a solvent or ethylene,? -Olefin and diene monomer itself can be used as a medium.

The solvent usable in the polymerization reaction may be an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent or a mixture thereof. The aliphatic hydrocarbon solvent may include, but is not limited to, butane, isobutane, pentane, hexane, heptane, octane, nonane, decane, Decane, undecane, dodecane, cyclopentane, methylcyclopentane, cyclohexane, and the like can be given. The aromatic hydrocarbon solvent may include, but not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, chlorobenzene, (Chlorobenzene), and the like. The halogenated aliphatic hydrocarbon solvent may include, but not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, 1,2-dichloroethane, 1,2-dichloroethane, and the like.

The process for producing an ethylene- alpha -olefin-diene terpolymer according to the present invention comprises polymerizing a monomer containing at least one ethylene, alpha -olefin and diene in the presence of the catalyst as described above. Examples of the? -Olefin monomer contained in the reactant include propylene, 1-butene, 1-hexene, 1-octene, 1-decene and 1-dodecene. Also, the diene monomer contained in the reactant may be selected from the group consisting of C4-C20 conjugated diene monomer, C5-C20 aliphatic non-conjugated diene monomer, C5-C20 cyclic non-conjugated diene monomer, and C6- And the like.

Preferably, the diene monomer is at least one monomer selected from the group consisting of butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,2-dimethyl-1,3-butadiene, 1,3-butadiene, 1,3-hexadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, C4-C20 conjugated diene-based monomers such as 3-pentadiene, 2,4-dimethyl-1,3-pentadiene and 3-ethyl-1,3-pentadiene; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-heptadiene, C20 aliphatic non-conjugated dienes such as 1,6-octadiene, 1,7-octadiene, 7-methyl-1,6-octadiene, 1,13-tetradicaradiene, Based monomers; Cyclohexadiene, picyclo [2.2.2] hept-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene- , Bicyclo [2.2.2] oct-2,5-diene, 4-vinylcyclohex-1-ene, bicyclo [2.2.1] hept-2,5-diene, bicyclopentadiene, methyltetrahydro C5-C20 cyclic non-conjugated diene-based monomer such as 5-allylbicyclo [2.2.1] hept-2-ene or 1,5-cyclooctadiene; And C6-C20 aromatic non-conjugated diene monomers such as 1,4-diallylbenzene and 4-allyl-1H-indene. However, in addition to the above-mentioned diene monomers, it is also possible to use 2,3-diisopropenylidene-5-norbornene, 2-ethylidene-3-isopropylidene- , 1,3,7-octatriene, 1,4,9-decatriene, and the like may be used.

On the other hand, the amount of the catalyst added in the polymerization reaction of the present invention is not particularly limited because it can be determined within a range in which the polymerization reaction of the monomers can sufficiently take place in accordance with slurry, liquid, vapor or massive processes. However, the amount of the catalyst and is based on the concentration of the central metal (M) in the main catalyst compound per unit volume (L) of the monomer (transition metal compound) 10 ^-8 to preferably a 1 mol / L, 10 ^-7 to 10 ^-1 mol / L it is more preferred, and 10 ^-7 to 10 ^-2 mol / L of it is further more preferable.

The polymerization reaction of the present invention may be carried out in a batch type, a semi-continuous type or a continuous type, preferably a continuous reaction.

The temperature and pressure conditions of the polymerization reaction of the present invention can be determined in consideration of the efficiency of the polymerization reaction depending on the kind of the reaction to be applied and the type of the reaction. However, the polymerization temperature is preferably 50 to 200 ° C, And the pressure may be 1 to 3,000 atm, preferably 1 to 1,000 atm.

In the present invention, the ethylene -? - olefin-diene terpolymer can increase the polymerization activity of ethylene,? -Olefin and diene monomer and exhibit a high molecular weight by using a catalyst containing a main catalyst compound and a cocatalyst compound.

The ethylene- -olefin-diene terpolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 30,000 to 800,000, and more preferably 60,000 to 500,000.

The molecular weight distribution (Mw / Mn) of the ethylene -? - olefin-diene terpolymer may be 1 to 15, preferably 1.5 to 10, more preferably 1.5 to 8.

The ethylene -? - olefin-diene terpolymer may have a density of 0.850 to 0.920 g / ml.

Hereinafter, a specific embodiment of the present invention will be described.

Except where otherwise noted, all ligand and catalyst synthesis experiments were carried out using standard Schlenk or glovebox techniques under a nitrogen atmosphere, and the organic solvents used for all reactions were refluxed under sodium metal and benzophenone to yield water And the product was distilled immediately before use. 1 ^H -NMR analysis of the synthesized ligand and catalyst was performed using Bruker 300 MHz at room temperature.

The polymerization solvent, n-hexane, was passed through a tube filled with 5A molecular sieve and activated alumina and bubbled with high purity nitrogen to sufficiently remove water, oxygen and other catalyst poison substances. All the polymerization was carried out by introducing the required amount of solvent, co-catalyst, monomers to be polymerized, etc. in a high-pressure reactor (autoclave) completely blocked with the external air and then adding the catalyst. The polymerized polymer was analyzed according to the following method.

(1) Melt index (MI)

Was measured using a device (manufacturer: Mirage, model: SD-120L) by applying ASTM D-1238 (condition E, 190 캜, 2.16 kg load).

(2) Content of 1-octene and 1,5-hexadiene in the copolymer

^& Lt; ¹ > H NMR (device name: Avance DRX400, manufacturer: Bruker).

(3) Weight average molecular weight (Mw) and molecular weight distribution (MWD)

And measured by GPC (Gel Permeation Chromatography, PL-GPC220, manufacturer: Agilent).

(4) Density

After treating the copolymer with an antioxidant, a sheet having a thickness of 3 mm and a radius of 2 cm was formed in a 180 ° compression mold, cooled to room temperature, and then measured using a machine (Toyoseiki, model: T-001).

(5) Tensile elongation and strength

And measured according to ASTM D412 using a universal material tester (Instron 4466).

(6) Shore D

And measured according to ASTM D2240 using a Shore hardness tester (Zwick / Roell).

Transition metal compound ( Tetramethylcyclopentadienyl Dimethylsilyl  2- methyl -4- (4-t- part Butylphenyl) Indeny  zirconium Dichloride ( Tetramethylcyclopentadienyl dimethylsilyl  2-methyl-4- (4-tert-butylphenyl) indenyl Zr  dichloride

1) Synthesis of dimethyl tetramethylcyclopentadienyl chlorosilane (dimethyl tetramethylcyclopentadienyl chlorosilane)

N-BuLi (2.5 M hexane solution) (170 ml) was slowly added dropwise at -10 ° C under a nitrogen atmosphere, followed by dropwise addition of 12 (trimethylsilyl) methylene chloride Lt; / RTI > for 1 hour. The temperature of the reaction solution was lowered to -10 ° C again, and then dimethyldichlorosilane (170 g) was added thereto. The mixture was stirred at room temperature for 12 hours for reaction, and then the reaction product was vacuum-dried. Hexane (500 ml) was added thereto to dissolve the reaction product. The reaction product was filtered through a Celite filter, and the filtered solution was vacuum-dried to obtain 70 g of dimethyl tetramethylcyclopentadienyl chlorosilane in the form of yellow oil (yield: 80%).

^{1 H-NMR (300 MHz,} CDCl3) δ 0.235 (s, 6H), 1.81 (s, 6H), 1.97 (s, 6H), 3.07 (s, 1H)

2) Synthesis of dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenyl silane (Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-tert-butylphenyl) indenyl silane)

The flask charged with toluene (200 ml), tetrahydrofuran (40 ml) and 2-methyl-4- (4-t-butylphenyl) indene (50 g) was cooled to -10 ° C and n-BuLi M hexane solution) (76 ml) was slowly added dropwise thereto, followed by stirring at room temperature for 12 hours. The temperature of the reaction mixture was lowered to -10 DEG C again, and then dimethyltetramethylcyclopentadienylchlorosilane (38 g) was added thereto, followed by stirring at room temperature for 12 hours. After completion of the reaction, water (400 ml) was added thereto, and the mixture was stirred at room temperature for 1.5 hours. Then, the mixture was extracted with toluene and vacuum dried to obtain dimethyltetramethylcyclopentadienyl 2- -Butylphenyl) indenylsilane (yield: 95%).

^{1 H-NMR (300 MHz,} CDCl3) δ 0.2-0.23 (d, 6H), 1.44 (s, 9H), 1.91 (s, 6H), 2.05-2.08 (d, 6H), 2.29 (s, 3H), 2.41 (s, 1 H), 3.76 (s, 1 H), 6.87 (s, 1 H)

3) Tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyl

Synthesis of zirconium dichloride (Tetramethylcyclopentadienyl dimethylsilyl 2-methyl-4- (4-tert-butylphenyl) indenyl Zr dichloride)

Dimethyl tetramethylcyclopentadienyl 2-methyl-4- (4-t-butylphenyl) indenylsilane (50 g), toluene (300 ml) and diethyl ether (100 ml) , And n-BuLi (2.5 M hexane solution) (90 ml) was slowly added dropwise. After dropwise addition, the reaction temperature was raised to room temperature, stirred for 48 hours, and then filtered. The obtained filtrate was vacuum-dried to obtain 40 g (yield 80%) of tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt as a solid, The next reaction was used.

Tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t-butylphenyl) indenyldilithium salt (40 g), toluene (40 ml) and ether (10 ml) were placed in a flask . In Flask # 2, a mixture of toluene (30 ml) and ZrCl ₄ (20 g) was prepared. The mixture of flask # 2 was slowly dropped into flask # 1 with a cannula, and then stirred at room temperature for 24 hours. After stirring, the mixture was vacuum-dried, extracted with methylene chloride (500 ml), filtered through a Celite filter, and then the filtrate was vacuum-dried. The resulting solid was washed with a 1: 3 mixture of methylene chloride and n-hexane (50 ml) and vacuum dried to obtain tetramethylcyclopentadienyldimethylsilyl 2-methyl-4- (4-t -Butylphenyl) indenylzirconium dichloride (the following formula 7) (yield: 60%).

¹ H-NMR (300 MHz, CDCl 3)? 1.09 (s, 3H), 1.202 (s, 3H), 1.346 (s, 9H), 1.887-1.911 s, 3H), 2.278 (s, 3H), 7.0-7.628 (m, 8H)

(7)

Example  One

After replacing the inside of the high-pressure reactor (internal capacity: 2 L, stainless steel) with nitrogen at room temperature, 1 L of normal hexane and 2 mL of triisobutyl aluminum were added. Subsequently, 10 mL of 1,5-hexadiene was added, and 90 mL of 1-octene and 135 g of ethylene gas were introduced. Thereafter, the reactor temperature was preheated to 80 DEG C, and 5 mL of a methylaluminoxane solution (10 wt% solution of methylaluminoxane in toluene, 15 mmol of Al, manufactured by Albemarle) as a co-catalyst compound, And the mixture was injected into the reactor, and polymerization was carried out for 5 minutes. When the polymerization was completed, the temperature was lowered to room temperature, and excess gas was discharged. Subsequently, the copolymer polymerization solution dispersed in the solvent was transferred to a vessel, and then dried in a vacuum oven at 80 DEG C for 15 hours or more to prepare an ethylene-1-octene-1,5-hexadiene terpolymer.

Example  2

Ethylene-1-octene-1,5-hexadiene terpolymer was prepared in the same manner as in Example 1 except that 5 mL of 1,5-hexadiene was used in Example 1.

Comparative Example  One

Ethylene-1-octene copolymer was prepared in the same manner as in Example 1, except that 1,5-hexadiene was not used in Example 1.

Comparative Example  2

A commercially available ethylene-1-octene copolymer (Engage 8450, manufactured by DuPont) was prepared.

The monomer content and physical properties of the copolymers prepared or prepared according to the above Examples and Comparative Examples were measured, and the results are shown in Table 1 below.

Polyolefin  Preparation of composition

Extruder (Brabender Plasticorder Extruder System, Model: 670237.001, Maker: Brabender ® GmbH & Co. KG) with the polypropylene (B-310, Maker: Lottechemical ) 85 parts by weight of the above Examples and Comparative Examples prepared according to or prepared 15 parts by weight of ethylene-1-octene-1,5-hexadiene or ethylene-1-octene copolymer were mixed at 180 DEG C at 100 rpm for 5 minutes and then extruded at 190 DEG C using a press molding machine Pressed for 8 minutes, and then cooled at room temperature for 5 minutes. The prepared polyolefin composition was allowed to stand for 24 hours or longer in a constant temperature and humidity chamber (25 ° C, 50% humidity), and the properties thereof were measured. The results are shown in Table 1 below.

Referring to Table 2, it can be seen that, in the production of an ethylene- -olefin-diene terpolymer by direct contact of ethylene, -olefin and diene using a specific metallocene catalyst system according to the present invention, Octene copolymers can be obtained. In addition, when 1,5-hexadiene is added, a polymer having improved tensile properties can be obtained as a result of formation of some crosslinked materials at the same time as polymerization. can confirm.

The preferred embodiments of the present invention have been described in detail above. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention Should be interpreted.

Claims (6)

Olefin-diene terpolymer, comprising the step of polymerizing a monomer containing ethylene, -olefin and a diene under a catalyst containing a transition metal compound represented by the following formula (1).
[Chemical Formula 1]

M is 2 and n is 0 and M is 0 and n is 1 when M is a divalent transition metal of Group 4 in the periodic table; is M and η ⁵ - is a cyclopentadienyl ring which can be combined, wherein the cyclopentadienyl ring (C1-C20) alkyl, (C3-C20) cycloalkyl, (C6-C20) aryl, tri (C1- (C6-C20) arylsilyl, (C6-C20) arylsilyl, (C1-C20) alkyldi It can be further substituted with one or more selected from the group consisting of alkenyl and; D is SiR ³ R ⁴ or (C2-C20) alkenylene; R ³ and R ⁴ are each independently hydrogen, (C1-C20) alkyl, (C3-C20) or cycloalkyl, or (C6-C20) aryl, wherein R ³ and R ⁴ are (C4-C7) are connected to the alkylene may form a ring; R ¹ is methyl; Ar is (C6 -C20) aryl; R ² is hydrogen, (C1-C20) alkyl, (C3-C20) cycloalkyl or (C6-C20) O And; wherein Ar and R ² are (C1-C7) alkylene, (C2-C7) alkenylene or a (C4-C7) are connected to the alkane diethoxy alkenylene may form a fused ring; X ¹ is halogen, (C1 -C20) alkyl, (C1-C20) alkoxy, (C3-C20) cycloalkyl, (C6-C20) aryl, (C6-C20) ^{aryloxy, -OSiR a R b R c,} -SR d, -NR e R ^f or R ^h and -PR ^g; R ^a to R ^h are each independently (C1-C20) alkyl, (C6-C20) aryl or (C3-C20) cycloalkyl; X ² is a neutral conjugated or non-conjugated (C 1 -C 20) alkyl, halo (C 1 -C 20) alkyl, cycloalkyl, aryl of the aryl, R ² , R ³ and R ⁴ of Ar are independently selected from the group consisting of halogen, May be further substituted with one or more substituents selected from the group consisting of (C3-C20) cycloalkyl, (C6-C20) aryl, (C1-C20) alkoxy and (C6-C20) The method according to claim 1,
Wherein the addition amount of the catalyst is 10 ^-8 to 1 mol / L based on the concentration of the central metal (M) in the transition metal compound per unit volume (L) of the monomer. The method according to claim 1,
Wherein the? -Olefin monomer is at least one selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, 1-decene and 1-dodecene, Wherein the monomer is at least one member selected from the group consisting of a monomer, an aliphatic non-conjugated diene monomer of C5-C20, a cyclic non-conjugated diene monomer of C5-C20, and an aromatic non-conjugated diene monomer of C6-C20. The method according to claim 1,
Wherein the ethylene -? - olefin-diene terpolymer has a weight average molecular weight (Mw) of 10,000 to 1,000,000. The method according to claim 1,
Wherein the ethylene -? - olefin-diene terpolymer has a molecular weight distribution (Mw / Mn) of 1 to 15. The method according to claim 1,
Wherein the ethylene -? - olefin-diene terpolymer has a density of 0.850 to 0.920 g / ml.