KR101367402B1 - Process for preparation of elastomeric polymer having high diene-based monomer content and high molecular weight - Google Patents

Abstract

The present invention relates to a method for producing an elastomer. Specifically, the method for preparing an elastomer according to the present invention includes the step of polymerizing ethylene, propylene and diene monomers in the presence of a catalyst composition comprising a transition metal compound. The method for preparing an elastomer according to the present invention can produce a high molecular weight ethylene-propylene-diene-based elastomeric copolymer, and has a high content of diene-based monomers.

Transition Metal Compounds, Elastomers

Description

PROCESS FOR PREPARATION OF ELASTOMERIC POLYMER HAVING HIGH DIENE-BASED MONOMER CONTENT AND HIGH MOLECULAR WEIGHT}

The present invention relates to a method for producing an elastomer. Specifically, the present invention relates to a method for producing an ethylene-propylene-diene-based elastic copolymer having high molecular weight and high content of diene monomer.

“Elastic polymer” was first defined in 1940, which is very fast, with properties similar to those of vulcanized natural rubber, for example, the ability to stretch more than twice its original length, and a length almost similar to its original length upon relaxation. Refers to synthetic thermoset higher polymers with the ability to shrink.

The most common polyolefin elastomers produced today are copolymers of ethylene and propylene (EP), and ternary interpolymers of ethylene, propylene and diene (EPDM).

EPM (ethylene-propylene copolymer) and EPDM (ethylene-propylene-diene terpolymer) were described in 1957 by Natta et al. In ethylene and propylene copolymerization using VOCl ₃ / Al (C ₆ H ₁₃ ) ₃ based catalysts. The discovery has led to continuous development and commercial production.

EPDM (ethylene-propylene-diene terpolymer) can be vulcanized with Sulfur, Peroxide, Radiation and the like. It is a synthetic rubber with excellent economic efficiency because it has excellent ozone resistance, weather resistance, heat resistance, solvent resistance, small specific gravity and high filling capacity of fillers and oils compared to other synthetic rubbers. The ethylene-propylene-diene terpolymer (EPDM) is mainly used for a wide variety of applications such as body sealing for automobiles, tire tubes, lakes, belts, electric wires, various industrial products, and other polyolefin modifiers.

EPM (ethylene-propylene copolymer) and EPDM (ethylene-propylene-diene terpolymer) are typically prepared using Ziegler catalyst systems comprising Group 4 or 5 and alkyl aluminum (halide) cocatalysts. Vanadium catalysts are common metals because they produce high molecular weight EP (D) M. These vanadium compounds are inexpensive but have low activity. In addition, vanadium-based catalysts generally exhibit good diene conversion at high ethylene compositions, but may not be suitable for preparing EPDM polymers at low ethylene content because they cannot effectively polymerize propylene and other long chain alpha olefins.

Recently, as a catalyst for olefin polymerization, a metallocene catalyst has been in the spotlight, and much research has been conducted on this. In general, polymers polymerized with a metallocene catalyst have a narrow molecular weight distribution and a uniform distribution of comonomers. In particular, by processing a polymer made using a metallocene catalyst, it is possible to make a film with higher strength and transparency than existing products. This advantage is because the metallocene catalyst has a uniform activity point, and is due to the molecular weight, molecular weight distribution, and comonomer distribution of the polymer.

Metallocene catalysts are more copolymerizable with long chain alpha-olefins than vanadium catalysts. The metallocene catalyst has the characteristics that the polymerization activity of the central metal sugar is higher than that of the vanadium catalyst, and the catalyst stability at high temperature is higher than that of the vanadium catalyst.

In general, the polymerization temperature in the solution polymerization of the vanadium catalyst is carried out at 30 ~ 70 ℃ has the advantage that the metallocene polymerization is possible at a high temperature of 80 ~ 120 ℃. However, metallocene catalysts show limitations in molecular weight. Due to the relatively fast termination (or chain transfer) reaction, metallocene catalysts tend to produce low molecular weight (when Mw is about 50,000 or less) polymers and copolymers at high temperatures.

EPM (ethylene-propylene copolymer) and EPDM (ethylene-propylene-diene terpolymer) generally require a weight average molecular weight of at least 60,000 to meet sufficient tensile strength useful for automobiles.

Kaminsky (J. Polm. Sci. Vol. 23, p2151-64 (1985)) introduced a soluble bis (cyclopentadienyl) zirconium dimethyl-aluminoacid catalyst system. The long reaction time resulted in high yield of high molecular weight EPDM (ethylene-propylene-diene terpolymer), but such a long residence time is economically unsuitable for commercial applications.

U.S. Pat. Nos. 4,871,705, 5,229,478, 5,491,207 describe EP (ethylene-propylene copolymer) or EPDM (using a bis-CP metallocene catalyst (i.e., a catalyst with two cyclopentadienyl or indenyl groups). Ethylene-propylene-diene terpolymer) is described. Bis-CP metallocene catalysts may be more stable than mono-CP metallocene catalysts under ethylene-propylene polymerization conditions, but bis-CP metallocenes are relatively difficult and expensive to synthesize.

Prior art metallocene / aluminoacid catalyst systems relating to the preparation of ethylene and alpha olefin elastomers typically describe producing low molecular weight polymers that are not suitable for use as commercial elastomers.

Also, diene monomers are generally more expensive monomer materials than ethylene or propylene. Therefore, in the production of EPM (ethylene-propylene copolymer) and EPDM (ethylene-propylene-diene terpolymer), high yield elastomers are produced within a reasonable polymerization time, and require high molecular weight and high diene conversion.

In order to solve the conventional problems as described above, the present invention provides a high yield of ethylene-propylene-diene-based elastomeric copolymer having a high molecular weight and high content of diene monomer in the presence of a catalyst composition comprising a transition metal compound To provide a way to.

The present invention is a method for producing an elastomer comprising the step of polymerizing ethylene, propylene and diene monomer in the presence of a catalyst composition comprising a transition metal compound,

The content of ethylene in the elastomer is 15 to 60% by weight, the content of propylene is 15 to 65% by weight and the content of the diene monomer provides a method for producing an elastomer, characterized in that more than 13% by weight 40% by weight. .

In addition, the present invention provides an elastomer prepared by the method for producing the elastomer.

As described above, the elastomer may be prepared using a catalyst composition including a transition metal compound known as a metallocene catalyst, and the polymer thus obtained may exhibit high molecular weight and high content of diene monomer.

Hereinafter, the present invention will be described in detail.

Method for producing an elastomer according to the present invention comprises the step of polymerizing ethylene, propylene and diene monomer in the presence of a catalyst composition comprising a transition metal compound, the content of ethylene in the elastomer is 15 to 60% by weight The content of propylene is 15 to 65% by weight and the content of the diene monomer is characterized in that more than 13% by weight 40% by weight or less.

In the method for preparing an elastomer according to the present invention, the transition metal compound may be represented by the following Chemical Formula 1.

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or metalloid radicals of Group 4 metals substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;

R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido Radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; Arylalkyl radicals having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

Unlike the conventional transition metal compound, the transition metal compound represented by Chemical Formula 1 is very stably maintained by a quinoline-based amido group in a pentagonal ring structure around a metal site, and thus structurally very accessible to monomers. It is easy and shows excellent reactivity in copolymerization between ethylene and a high steric hindrance monomer by using a catalyst composition comprising the transition metal compound. Therefore, the transition metal compound represented by Formula 1 has an advantage that copolymerization of propylene and diene is superior to other transition metal compounds, and particularly, the production of EP and EPDM is possible at high temperatures of 100 ° C. or higher.

A more detailed description of the transition metal compound represented by Formula 1 is as follows.

In Formula 1, hydrocarbyl is a monovalent group in a form in which hydrogen atoms are removed from hydrocarbons, and includes ethyl, phenyl, and the like.

In Chemical Formula 1, the metalloid is a metal and an element showing intermediate properties between metal and nonmetal, and include arsenic, boron, silicon, tellurium, and the like.

Among the compounds of the formula (1), the transition metal compound is preferably a transition metal compound represented by the following formula (2) or (3) for controlling the electronic and stereoscopic environment around the metal.

In Chemical Formulas 2 and 3,

R4 and R5 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Or a silyl radical;

R6 may be the same or different and are each independently selected from the group consisting of hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido radicals; Two or more R < 6 > among the R < 6 > may be linked to each other to form an aliphatic or aromatic ring;

Q3 and Q4 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; Or an arylamido radical having 6 to 20 carbon atoms;

M is a Group 4 transition metal.

In the above formula (1), more preferred compounds for controlling the electronic stereoscopic environment around the metal are transition metal compounds having the following structures.

In the above formula,

R7, which may be the same or different, are each independently selected from hydrogen or a methyl radical,

Q5 and Q6 may be the same or different and are each independently selected from a methyl radical, a dimethylamido radical, or a chloride radical.

In the method for preparing an elastomer according to the present invention, the catalyst composition may further include one or more cocatalysts selected from the compounds represented by the following Chemical Formulas 4, 5 or 6.

- [Al (R &_lt; 8 >) - O] _n -

In Chemical Formula 4,

R8 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more;

D (R 8) ₃

In Formula 5,

R8 is as defined in Formula 4 above;

D is aluminum or boron;

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 6,

L is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same or different from each other, and each independently is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, unsubstituted or substituted with one or more hydrogen atoms, halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy. .

Examples of the compound represented by the formula (4) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

The compound represented by the general formula (6) includes a non-coordinating anion which is compatible with a cation which is a Bronsted acid. Preferred anions are those that are relatively large in size and contain a single coordinating complex comprising a metalloid. In particular, compounds containing a single boron atom in the anion moiety are widely used. From this viewpoint, the compound represented by the formula (6) is preferably an anion-containing salt containing a coordinating complex containing a single boron atom.

Specific examples of such compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate and tripropylammonium tetrakis (pentafluorophenyl) in the case of trialkylammonium salts. Borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl Borate, N, N-dimethylanilinium n-butyltris (pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4 -(t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-triisopropylsilyl) -2,3,5,6- Tetrafluorophenyl) borate, N, N-dimethylanilinium Tafluorophenoxycitries (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis ( Pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropyl Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethyl Anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl Borei , Decyldimethylammonium tetrakis (pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis (Pentafluorophenyl) borate, octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldidecylammonium tetrakis (pentafluorophenyl) borate, Methyldidodecylammonium tetrakis (pentafluorophenyl) borate, methylditetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyldioctadecylammonium tetra Kis (pentafluorophenyl) borate, methyldiecosylammonium tetrakis (pentaflu Rophenyl) borate, tridecylammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, tritetradecylammonium tetrakis (pentafluorophenyl) borate, trihexadecylammonium Tetrakis (pentafluorophenyl) borate, trioctadecylammonium tetrakis (pentafluorophenyl) borate, trieicosylammonium tetrakis (pentafluorophenyl) borate, decyldi (n-butyl) ammonium tetrakis (penta Fluorophenyl) borate, dodecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, octadecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-didodecylanyl Linium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecylanilinium tetrakis (pentafluorophenyl) borate, methyldi (dodecyl) ammonium tetrakis (pen Tafluorophenyl) borate etc. are mentioned.

Examples of dialkylammonium salts include di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate and the like.

Examples of the carbonium salt include tropylium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, benzene (diazonium) tetrakis (pentafluorophenyl) .

Particularly preferred compounds include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, tributylammonium tetrakis (pentafluorophenyl) borate, di (octadecyl) methylammonium tetrakis (pentafluorophenyl) ) Borate, di (octadecyl) (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylmethylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis For example.

In the method for producing an elastomer according to the present invention, the catalyst composition comprises the steps of contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 4 or Formula 5 to obtain a mixture; And it may be prepared from a method comprising the step of adding a compound represented by the formula (6) to the mixture.

In the catalyst composition, the molar ratio of the transition metal compound represented by the formula (1) to the compound represented by the formula (4) is preferably 1: 10 to 1: 10,000, and the transition metal compound represented by the formula (1) to the formula (5) Or the molar ratio of the compound represented by 6 is preferably 1: 1 to 1: 25, but is not limited thereto.

The solvent used in the polymerization method of the present invention is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, such as pentane, hexane, heptane, nonane, decane and their isomers and toluene, benzene, Isopar ^TM E, (Exxon Chemicals, Aromatic hydrocarbon solvents such as Inc.). The solvent used for the polymerization is preferably used by removing a small amount of water or air that acts as a catalyst poison through a purification process, and may be carried out by treating a small amount of alkyl aluminum.

In the method for producing an elastomer according to the present invention, the diene monomer may include a diene monomer selected from the group consisting of conjugated diene monomers and nonconjugated diene monomers.

As the conjugated diene monomer, butadiene, isoprene, 2,3-dimethylbutadiene-1,3, 1,2-dimethylbutadiene-1,3, 1,4-dimethylbutadiene-1,3, 1-ethylbutadiene-1 , 3, 2-phenylbutadiene-1,3, hexadiene-1,3, 4-methylpentadiene-1,3, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 2,4 -Dimethyl-1,3-pentadiene, 3-ethyl-1,3-pentadiene, and the like, and 1,3-pentadiene is more preferred, but is not limited thereto.

Examples of the non-conjugated diene monomers include aliphatic diene monomers, cyclic diene monomers, aromatic diene monomers, and triene monomers.

As the aliphatic diene monomer, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,5-hexadiene, 1,6-heptadiene, 6-methyl- 1,5-heptadiene, 1,6-octadiene, 1,7-octadiene, 7-methyl-1,6-octadiene, 1,13-tetradecadiene, 1,19-eicosadiene, etc. are mentioned. But it is not limited thereto.

Examples of the cyclic diene monomers include 1,4-cyclohexadiene, bicyclo [2.2.1] hept-2,5-diene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5 -Vinyl-2-norbornene, bicyclo [2,2,2] oct-2,5-diene, 4-vinylcyclohex-1-ene, bicyclo [2,2,2] oct-2,6- Dienes, 1,7,7-trimethylbicyclo- [2,2,1] hept-2,5-diene, dicyclopentadiene, methyltetrahydroindene, 5-allylbicyclo [2,2,1] Hept-2-ene, 1,5-cyclooctadiene, and the like, but are not limited thereto.

Examples of the aromatic diene monomer include 1,4-diallylbenzene, 4-allyl-1H-indene, and the like, but are not limited thereto.

The triene monomers include 2,3-diisopropenylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene , 1,3,7-octatriene, 1,4,9-decatriene, and the like, but are not limited thereto.

As the non-conjugated diene monomer, 5-ethylidene-2-norbornene, 1,4-hexadiene, dicyclopentadiene are more preferred, but are not limited thereto.

In the method for producing an elastomer according to the present invention, the elastomer may be an elastomer including ethylene, propylene, and diene monomers.

In the method for producing an elastomer according to the present invention, the content of ethylene in the elastomer is 15 to 60% by weight, the content of propylene is 15 to 65% by weight and the content of the diene monomer is more than 13% by weight 40% by weight or less It is characterized by. In addition, the content of ethylene in the elastomer is 30 to 50% by weight, the content of propylene is 30 to 50% by weight and the content of the diene monomer is more preferably 13% by weight to 35% by weight or less.

In the method for producing an elastomer according to the present invention, the polymerization may be carried out under conventionally known conditions, that is, a temperature of 0 to 250 ° C. and a pressure of atmospheric pressure to 1,000 atm. In addition, suspension, solution, slurry, gas phase, and other polymerization method conditions may be used if desired, but solution polymerization method conditions, in particular, continuous solution polymerization method are preferred. In order to be used for continuous solution polymerization, polymerization temperature is suitable 70-160 degreeC. Supports may be used, but preferably catalysts are used in the homogeneous technique, ie they are dissolved in solution.

The present invention can be applied not only to a single reactor but also to two or more multistage reactors. Two or more multi-stage reactors may be used as a manufacturing method having a wide molecular weight distribution by varying the reaction conditions in each reactor to induce different molecular weights, but as disclosed in US Pat. No. 6,329,477, EPDM (ethylene-propylene-diene terpolymer) Copolymer) may also be used as a means to increase the conversion of the diene monomer.

The present invention also provides an elastomer prepared by the method for producing an elastomer according to the present invention.

The elastomer according to the present invention is characterized by high incorporation, high conversion, and high activity of comonomers such as propylene and diene monomers. In particular, it is difficult to increase the degree of incorporation of the diene monomer in the prior art for technical and economic reasons, in the present invention, by using a catalyst composition comprising a transition metal compound represented by Formula 1, the degree of incorporation of the diene monomer, There is a feature that can easily increase the conversion rate.

The molecular weight distribution (Mw / Mn) of the elastomer according to the present invention may be 1.5 to 15, preferably 1.8 to 10, and more preferably 2 to 6.

The weight average molecular weight (Mw) of the elastomer according to the invention may be 10,000 to 1,000,000, preferably 20,000 to 800,000, more preferably 40,000 to 600,000, and particularly preferably 60,000 to 500,000.

In addition, the density of the elastomer may be measured according to ASTM D-792, the density of the elastomer according to the present invention may be 0.850 ~ 0.895 g / cm ³ , preferably 0.853 ~ 0.885 g / cm ³ , It is more preferable that it is 0.855-0.875 g / cm <^3> .

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

< Example >

As for the molecular weight distribution of the polymer, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using PL-GPC 220 manufactured by Polymer Laboratory.

< Ligand  And synthesis of metal compounds>

Organic reagents and solvents were purchased from Aldrich and Merck and purified by standard methods. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. Spectra and schematics were obtained using 400 MHz nuclear magnetic resonance (NMR) and X-ray spectroscopy to demonstrate the structure of the compounds.

The preparation method of the catalyst formula 1 used in the examples herein is described in Korean Patent KR 0,820,542, Korean Patent Application No. 2007-0042084.

Dow's dimethylsilyl (t-butylamido) (tetramethylcyclopentadienyl) titanium dimethyl (Constrained-Geometry Catalyst, CGC), a catalyst used in Comparative Examples, was used in the ethylene copolymerization reaction.

< Example  1>

< Example  1-1> lithium Carbamate ( Lithium carbamate ) (2)

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a flask. The flask was immersed in a -78 ° C low temperature bath made of dry ice and acetone, stirred for 30 minutes, and then normal butyllithium (39.3 mL, 2.5 M hexane solution, 98.24 mmol) was introduced into a syringe under a nitrogen atmosphere. A light yellow slurry formed. After stirring for 2 hours, it was raised to room temperature while removing the butane gas formed. The flask was again immersed in a -78 ° C. low temperature bath to lower the temperature, and then CO ₂ gas was added thereto. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler to raise the temperature to room temperature while removing carbon dioxide gas, followed by vacuum to remove excess CO ₂ gas and solvent. The flask was transferred to a dry box, pentane was added thereto, stirred and filtered to obtain a white solid compound. The compound is a compound in which diethyl ether is coordinated. At this time, the yield was 100%.

¹ H NMR (C ₆ D ₆ , C5D5N): δ 8.35 (d, J = 8.4 Hz, 1H, CH), δ 6.93-6.81 (m, 2H, CH), δ 6.64 (t, J = 7.4 Hz, 1H , CH), δ 3.87 (br, s, 2H, quin-CH ₂ ), δ 3.25 (q, J = 7.2 Hz, 4H, ether), δ 2.34 (br s, 2H, quin-CH2), δ 1.50 ( br s, 2H, quin-CH 2), δ 1.90 (t, J = 7.2 Hz, 6H, ether) ppm.

< Example  1-2> 8- (2,3,4,5- Tetramethyl -1,3- Cyclopentadienyl ) -1,2,3,4- Tetrahydroquinoline (8- (2,3,4,5- Tetramethyl -1,3- cyclopentadienyl ) -1,2,3,4- tetrahydroquinoline )

A lithium carbamate (2) compound (8.47 g, 42.60 mmol) was placed in the flask. Tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added sequentially. The flask was immersed in a -20 ° C. low temperature bath made of acetone and a small amount of dry ice, stirred for 30 minutes, and then tert-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added thereto. At this time, it turned red. Stir for 6 hours while maintaining -20 ° C. CeCl ₃ · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) and tetramethylcyclopentinone (5.89 g, 42.60 mmol) dissolved in tetrahydrofuran were mixed in a syringe and then introduced into a flask under nitrogen atmosphere. After slowly raising the temperature to room temperature, the thermostat was removed after 1 hour to raise the temperature to room temperature. After addition of water (15 mL), ethyl acetate was added and filtered to obtain a filtrate. The filtrate was transferred to a separatory funnel, and hydrochloric acid (2N, 80 mL) was added thereto, followed by shaking for 12 minutes. After neutralizing with saturated aqueous sodium hydrogen carbonate solution (160 mL), the organic layer was extracted. Anhydrous magnesium sulfate was added to this organic layer to remove water and filtered, and the filtrate was taken out and the solvent was removed. Column chromatography gave a yellow oil. Hexane: toluene (v / v, 10: 1), hexane: ethyl acetate (v / v, 10: 1), yield was 40%.

¹ H NMR (C ₆ D ₆ ): δ 1.00 (br d, 3H, Cp-CH ₃ ), 1.63-1.73 (m, 2H, quin-CH ₂ ), 1.80 (s, 3H, Cp-CH ₃ ), 1.81 (s, 3H, Cp-CH ₃ ), 1.85 (s, 3H, Cp-CH ₃ ), 2.64 (t, J = 6.0 Hz, 2H, quin-CH ₂ ), 2.84-2.90 (br, 2H, quin -CH ₂ ), 3.06 (br s, 1H, Cp-H), 3.76 (br s, 1H, NH), 6.77 (t, J = 7.2 Hz, 1H, quin-CH), 6.92 (d, J = 2.4 Hz, 1H, quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm.

< Example  1-3> lithium 1- (1- methyl -2,3,4- Trihydroquinoline -8-yl) -2,3,4,5-tetramethylcyclopentadienide ( Lithium  1- (1- methyl -2,3,4- trihydroquinolin -8- yl ) -2,3,4,5- tetramethylcyclopentadienide )

8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-trihydroquinoline (2 g, 7.89 mmol) in methanol (42 mL) Into a formaldehyde 37% aqueous solution (0.88 mL, 11.8 mmol) was added and stirred at room temperature for 30 minutes. Dicaborane (decaborane, 0.29 g, 2.37 mmol) was added to the mixture, followed by further stirring at room temperature for 1 hour. The resulting compound was filtered through a silica pad using hexane and ethyl acetate (v: v = 10: 1) solvent. The compound obtained by removing the solvent of the filtered solution was transferred to a flask, pentane (50 mL) was added, and the temperature was lowered to -78 ° C. Normal butyllithium (3.2 mL, 2.5 M hexane solution, 7.89 mmol) at -78 ° C was introduced by syringe under nitrogen atmosphere. After slowly warming to room temperature, the mixture was further stirred at room temperature for 3 hours. The reaction was filtered under nitrogen atmosphere, washed twice with pentane (10 mL) and dried under vacuum. A yellow solid lithium salt was obtained (0.837 g, 39%).

¹ H NMR (pyr-d5): δ 7.31 (br s, 1H, CH), δ 7.10-6.90 (m, 1H, CH), δ 6.96 (s, 1H, CH), δ 3.09 (m, 2H, quinoline -CH ₂ ), δ 2.77 (t, J = 6 Hz, 2H, quinoline-CH ₂ ), δ 2.51-2.11 (m, 15H, Cp-CH ₃ , N-CH ₃ ), δ 1.76 (m, 2H, quinoline -CH ₂ ) ppm.

< Example  1-4> Bis [1- (1- methyl -2,3,4- Trihydroquinoline -8-day) -2,3,4,5- Tetramethylcyclopentadienyl ] Titanium (IV) Dimethyl Compound

In a dry box, TiCl ₄ DME (429 mg, 1.53 mmol) and diethyl ether (25 mL) were added to a flask, and MeLi (1.9 mL, 1.6 M diethyl ether solution, 3.07 mmol) was slowly added thereto while stirring at -30 ° C. After stirring for 15 minutes, the lithium salt compound (838 mg, 3.06 mmol) obtained in Example 1-3 was placed in a flask. Stir for 3 hours while raising the temperature to room temperature. After the reaction was completed, vacuum was applied to remove the solvent, dissolved in pentane, filtered, and the filtrate was extracted. Pentane was removed by vacuum to obtain a titanium complex.

¹ H NMR (C ₆ D ₆ ): δ 6.83 (d, J = 7.2 Hz, 2H, CH), δ 6.78 (d, J = 7.6 Hz, 2H, CH), δ 6.73 (t, J = 7.4 Hz, 2H, CH), δ 2.80 (m, 4H, quin-CH ₂ ), δ 2.52 (t, J = 6.4 Hz, 4H, quin-CH ₂ ), δ 2.26 (s, 6H, N-CH ₃ ), δ 1.96 (s, 12H, Cp-CH ₃ ), δ 1.85 (s, 12H, Cp-CH ₃ ), δ 1.50 (m, 4H, quin-CH ₂ ), δ 1.26 (s, 6H, Ti-CH ₃ ) ppm.

< Example  2>

< Example  2-1> 6- methyl -8- (2,3,4,5- Tetramethyl -1,3- Cyclopentadienyl ) -1,2,3,4- Tetrahydroquinoline

Lithium carbamate compound and 6-methyl-8- (2,3,4,5-tetramethyl-1 in the same manner as in Example 1 using 6-methyl-1,2,3,4-tetrahydroquinoline , 3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline was prepared. The yield was 34%.

¹ H NMR (CDCl ₃ ): δ 6.70 (s, 1H, CH), δ 6.54 (s, 1H, CH), δ 3.71 (br s, 1H, NH), δ 3.25-3.05 (m, 3H, Cp− CH, quinoline-CH ₂ ), δ 2.76 (t, J = 6.4 Hz, 2H, quinoline-CH ₂ ), δ 2.19 (s, 3H, CH ₃ ), δ 1.93-1.86 (m, 2H, quinoline-CH ₂ ), δ 1.88 (s, 3H, Cp-CH ₃ ), δ 1.84 (s, 3H, Cp-CH ₃ ), δ 1.74 (s, 3H, Cp-CH ₃ ), δ 0.94 (br d, J = 6.8 Hz, 3H, Cp-CH ₃ ) ppm.

< Example  2-2> lithium 1- (6, N-dimethyl-1,2,3,4- Tetrahydroquinoline -8-day) -2,3,4,5- Tetramethylcyclopentadienide

6-methyl-8- (2,3,4,5-tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline in the same manner as in Example 1 above Prepared.

¹ H NMR (pyr-d5): δ 7.05 (br s, 1H, CH), δ 6.73 (s, 1H, CH), δ 6.96 (s, 1H, CH), δ 3.08 (m, 2H, quinoline-CH ₂ ), δ 2.76 (t, J = 6.4 Hz, 2H, quinoline-CH ₂ ), δ 2.57-2.25 (m, 18H, Cp-CH ₃ , Ph-CH ₃ , N-CH ₃ ), δ 1.76 (m , 2H, quinoline-CH ₂ ) ppm.

< Example  2-3> bis [1- (6, N-dimethyl-1,2,3,4- Tetrahydroquinoline -8-day) -2,3,4,5- Tetramethylcyclopentadienyl ] titanium( lV Dimethyl compound

Lithium salt compound prepared above (lithium 1- (N-methyll-1,2,3,4-tetrahydroquinolin-8-yl) -2,3,4,5-tetramethylcyclopentadienyl) It was prepared in the same manner as in Example 1 above.

¹ H NMR (C ₆ D ₆ ): δ 6.65 (m, 4H, CH), δ 2.83 (m, 4H, quin-CH ₂ ), δ 2.54 (t, J = 7.2 Hz, 4H, quin-CH ₂ ) , δ 2.28 (s, 6H, N-CH ₃ ), δ 2.14 (s, 6H, Ph-CH ₃ ), δ 1.99 (s, 12H, Cp-CH ₃ ), δ 1.87 (s, 12H, Cp-CH3 ), δ 1.52 (m, 4H, quin-CH ₂ ), δ 1.28 (s, 6H, Ti-CH ₃ ) ppm.

< Comparative Example  1> Me ₂ N ( Me ) Si (? ⁵ - C ₅ H ₄ ) (t- Butyl amido ) TiMe ₂

20 mmole of LiCp (Lithium Cyclopentadienide) was weighed into the reaction vessel. After adding 50 mL of THF, the reaction vessel was cooled to -78 ° C. Excess MeSiCl ₃ (1.5 equiv) was added to the reaction vessel. It stirred for 12 hours, heating up the temperature of reaction container to normal temperature. After removing the THF from the reaction solution, 30mL of hexane was added to filter to remove LiCl. THF 50mL was added to the reaction vessel from which hexane was removed, and then cooled to -78 ° C. After adding 2 equivalents of t-butylamine (40mmole), the reaction vessel was stirred for 12 hours while the temperature was raised. After removing THF, 30 mL of hexane was added to remove the t-butylamine salt through a filter. Hexane was removed in vacuo and weighed in Glove-box. THF 50 mL was added to the reaction vessel, the reaction temperature was cooled to -78 ° C, and 2 equivalents of dimethylamine was added thereto. It stirred for 12 hours, heating up reaction container to room temperature. After 12 hours of reaction, THF was removed in vacuo, and then 30 mL of hexane was added to remove the amine salt. The synthesized ligand was upgraded to Glove-box, 4.4 equivalents of triethylamine was added in toluene solvent, 2 equivalents of n-BuLi was added at a reaction temperature of -78 ° C, and the reaction temperature was stirred at -78 ° C for 12 hours. It was. After 12 hours of reaction, 1 equivalent of TiCl ₄ was added at a reactor temperature of -78 ° C. After stirring for 12 hours while raising the temperature of the reaction solution to room temperature, toluene as a reaction solvent was removed in vacuo, and then hexane was added to filter to remove LiCl. The hexane solution obtained through the filter was left at -20 ° C to obtain a yellow solid (89% yield).

¹ H NMR (400.13 MHz, CDCl ₃ , ppm): δ = 7.00 (m, 1H, C ₅ H ₄ ), 6.87 (m, 1H, C ₅ H ₄ ), 6.03 (m, 1H, C ₅ H ₄ ) , 5.92 (m, 1H, C ₅ H ₄ ), 2.77 (s, 6H, (CH ₃ ) ₂ N), 1.52 (s, 9H, (CH ₃ ) ₃ CN), 0.59 (s, 3H, CH ₃ Si ); ¹³ C NMR (100.62 MHz, CDCl ₃ , ppm): δ = 130.86, 125.99, 116.66, 113.76, 110.92, 37.36, -5.67;

< Example  3 to 4 and Comparative Example  2 to 6> ethylene, propylene and 5- Ethylidene -2- Nobonen Samwon  Copolymer

In the polymerization, 1,000 mL of a hexane solution was first put in a 2 L autoclave, then an appropriate amount of 5-ethylidene-2-norbornene (ENB) was added, and 0.8 M of propylene was added thereto. The pressure in the reactor was then maintained at 16 bar with ethylene while preheating the reactor temperature to 115 ° C. After saturation of the ethylene gas, the 50 mL catalyst vessel was treated with a triisobutylaluminum compound (125 mmol) treated with a catalyst (5 mmol) and dimethylanilinium tetrakis (pentafluorophenyl) borate promoter solution (25 mmol) in a 50 mL catalyst vessel. Was injected into the catalyst vessel, and the copolymerization reaction was carried out for 8 minutes while argon was added into the catalyst vessel. After completion of the reaction, the ethylene gas was shut off, the remaining ethylene gas was removed, and then the copolymer solution was added to excess ethanol to precipitate the copolymer. The resulting copolymer was washed with ethanol 2 to 3 times, respectively, and then the obtained copolymer was filtered to remove the solvent and dried under reduced pressure in a 60 ° C vacuum oven.

The physical properties of the polymers prepared according to Examples 3 to 7 and Comparative Examples 2 to 6 are shown in Table 1 below.

In Table 1, the catalyst of the example used was 1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-N] titanium dimethyl, and the catalyst of the comparative example was dimethylsilyl. (t-butylamido) (tetramethylcyclopentadienyl) titanium dimethyl was used.

As shown in Table 1, the catalyst of the present example forms an elastomer having a high molecular weight in the preparation of EDPM (ethylene-propylene-diene terpolymer) compared to the catalyst of the comparative example. In addition, the content of 5-ethylidene-2-norbornene in the polymer is high, and the conversion of diene is relatively high.

1 is a view showing the content of the diene monomer in the elastomer according to the Examples and Comparative Examples of the present invention.

2 is a view showing the weight average molecular weight of the elastomer according to the Examples and Comparative Examples of the present invention.

Claims (10)

In the presence of a catalyst composition comprising a transition metal compound represented by the formula (1), a method for producing a ternary elastomer comprising the step of polymerizing ethylene, propylene and diene monomers, The content of ethylene in the elastomer is 15 to 60% by weight, the content of propylene is 15 to 65% by weight and the content of the diene monomer is more than 13% by weight up to 40% by weight, the density is 0.850 ~ 0.895g / cm ³ Method for producing a ternary elastomer, characterized in that: [Formula 1]

In Formula 1, R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms; R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido Radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring; CY1 is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring; M is a Group 4 transition metal; Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms. delete The method of claim 1, wherein the transition metal compound represented by Formula 1 is a transition metal compound represented by Formula 2 or Formula 3 below: (2)

(3)

In Chemical Formulas 2 and 3, R4 and R5 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Or a silyl radical; R6 may be the same or different and are each independently selected from the group consisting of hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or amido radicals; Two or more R &lt; 6 &gt; among the R &lt; 6 &gt; may be linked to each other to form an aliphatic or aromatic ring; Q3 and Q4 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; Or an arylamido radical having 6 to 20 carbon atoms; M is a Group 4 transition metal. The method of claim 1, wherein the catalyst composition further comprises at least one cocatalyst selected from the compounds represented by the following Chemical Formulas 4, 5 or 6: [Chemical Formula 4] - [Al (R &_lt; 8 &gt;) - O] _n - In Chemical Formula 4, R8 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen; n is an integer of 2 or more; [Chemical Formula 5] D (R 8) ₃ In Formula 5, R8 is as defined in Formula 4 above; D is aluminum or boron; [Chemical Formula 6] [LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^- In Formula 6, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy . The method according to claim 4, wherein the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 4 is 1: 10 to 1: 10,000. The method of claim 4, wherein the molar ratio of the transition metal compound represented by Formula 1 to the compound represented by Formula 5 or 6 is 1: 1 to 1: 25. The method of claim 1, wherein the diene monomer is selected from the group consisting of 5-ethylidene-2-norbornene, 1,4-hexadiene, and dicyclopentadiene. The method of claim 1, wherein the polymerizing of the ethylene, propylene and diene monomers is carried out at 70 to 160 ° C. A ternary elastomer prepared by the method for producing an elastomer according to any one of claims 1 and 3 to 8. The ternary elastomer according to claim 9, wherein the weight average molecular weight (Mw) of the elastomer is 10,000 to 1,000,000.

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