KR20170075365A - Elastic diene terpolymer and preparation method thereof - Google Patents

Abstract

The present invention relates to a ternary elastomeric copolymer having a long chain branch capable of simultaneously satisfying excellent processability and flexibility (flexibility) and a method for producing the same. The ternary elastomeric copolymer is a copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene,
i) a weight average molecular weight measured by GPC of from 10,000 to 100,000,
ii) The absorbance measured by Colorimeter may have a value of -5 to +5.

Description

TECHNICAL FIELD [0001] The present invention relates to a ternary elastomeric copolymer including a diene, and a method for producing the same. BACKGROUND ART [0002]

The present invention relates to a ternary elastomeric copolymer which is a copolymer of ethylene, an alpha olefin and a diene, and a process for producing the same. More specifically, the present invention relates to a ternary elastomeric copolymer capable of simultaneously satisfying low molecular weight and excellent transparency, and a method for producing the same.

EPDM rubbers, which are three-component elastomeric copolymers such as alpha-olefins such as ethylene and propylene and dienes such as ethylidene norbornene, have a molecular structure that does not have an unsaturated bond in the main chain, and are superior in weather resistance, chemical resistance and heat resistance to general conjugated diene rubbers And has excellent characteristics.

Previously, such a ternary elastomer such as EPDM rubber has been produced by copolymerizing three kinds of monomers using a catalyst containing a vanadium compound, for example, a vanadium-based Ziegler-Natta catalyst. However, such a vanadium-based catalyst needs to use an excess amount of catalyst with a low catalytic activity, which results in a high residual metal content in the copolymer, which causes a problem in that the produced copolymer shows color. Accordingly, catalyst removal and decolorization processes are required after the production of the copolymer, and deterioration of heat resistance, generation of foreign matter, or inhibition of the vulcanization reaction may be caused by residual catalyst components in the resin. In addition, the production of a ternary elastomeric copolymer using the vanadium compound-containing catalyst is not easy to control the reaction temperature due to low polymerization activity and low-temperature polymerization conditions, and it is difficult to control the amount of comonomers to be inhaled such as propylene and diene, It is true that it was difficult to control the molecular structure. Therefore, when a vanadium-based catalyst is used, the production of a three-component elastomer having various physical properties has been limited. Due to these problems, recently, a method of producing a ternary elastomeric copolymer such as an EPDM rubber by using a metallocene type transition metal catalyst of the metallocene type instead of a vanadium-based Ziegler-Natta catalyst has been developed.

These four-group transition metal catalysts exhibit high polymerization activity in the olefin polymerization and have the advantage of copolymerization of various comonomers. For example, U.S. Patent No. 5,229,478, U.S. Patent No. 6,545,088, and Korean Patent No. 0488833 disclose various metallocene group 4 transition metal catalysts obtained from ligands such as cyclopentadienyl, indenyl or fluorenyl, , It is disclosed that a ternary elastomer having a large molecular weight can be obtained with excellent polymerization activity.

However, when three kinds of monomers are copolymerized using such a conventional four-group transition metal catalyst, the repeating units derived from each monomer in the copolymer chain due to the high reactivity of alpha-olefins with comonomers, etc., The disadvantage that the distribution of the difficult dienes becomes uneven is generated.

Accordingly, there is a continuing need to develop a ternary elastomeric copolymer which can simultaneously satisfy both low molecular weight and excellent transparency while having a high content of dienes, and a manufacturing method capable of producing the copolymer with high productivity and yield.

U.S. Patent No. 5,229,478 U.S. Patent No. 6,545,088 Korean Patent No. 0488833

Accordingly, the present invention provides a ternary elastomeric copolymer which can simultaneously satisfy low molecular weight and excellent transparency.

The present invention also provides a process for producing a ternary elastomeric copolymer capable of producing the ternary elastomeric copolymer with high productivity.

The present invention relates to a copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene obtained in the presence of a Group 4 transition metal catalyst, the copolymer comprising: i) a weight average molecular weight measured by GPC of 10,000 to 100,000; ii) Is -5 to +5.

The present invention also provides a catalyst composition comprising 20 to 80% by weight of ethylene, 15 to 75% by weight of ethylene, Of an alpha-olefin having 3 to 20 carbon atoms and 0.5 to 20% by weight of a diene, based on the total weight of the three-component elastomeric copolymer.

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R ₁ to R ₁₃ 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; Two adjacent two of R ₁ to R ₁₃ may be connected to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form an aliphatic ring or an aromatic ring ;

M is a Group 4 transition metal;

Q ₁ and Q _{2, which} may be the same or different, 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.

Hereinafter, the ternary elastomeric copolymer according to a specific embodiment of the present invention and a method for producing the same will be described in detail.

First, the term "ternary elastomeric copolymer" used in the present specification can be defined as follows unless otherwise specified. The "ternary elastomeric copolymer" may refer to any elastic copolymer (for example, a crosslinkable random copolymer) in which three kinds of monomers such as ethylene, an alpha olefin having 3 to 20 carbon atoms, and a diene are copolymerized have. Representative examples of such "ternary elastomeric copolymer" include EPDM rubber which is a copolymer of ethylene, propylene and a diene. However, it should be noted that such a " ternary elastomeric copolymer "does not refer to only a copolymer of three monomers, and one or more monomers belonging to the category of alpha olefins and one or more monomers belonging to the category of dienes, It is to be understood that the present invention can include any elastic copolymer. For example, an elastic copolymer obtained by copolymerizing ethylene with two types of alpha-olefins of propylene and 1-butene, and two dienes such as ethylidene norbornene and 1,4-hexadiene is also an ethylene- , And three kinds of monomers respectively belonging to the category of dienes are copolymerized, and thus can be classified into the above-mentioned "ternary elastomeric copolymer ".

On the other hand, according to one embodiment of the present invention, as a copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene obtained in the presence of a transition metal of Group 4,

i) a weight average molecular weight measured by GPC of from 10,000 to 100,000,

ii) a ternary elastomeric copolymer having an absorbance of -5 to +5 as measured by Colorimeter.

The ternary elastomeric copolymer of this embodiment is a copolymer of three kinds of monomers such as ethylene, alpha olefin and diene in a predetermined content range, and has a molecular weight of about 10,000 to 100,000, or about 15,000 to 80,000, or about 20,000 to 80,000 Of the weight average molecular weight. These small weight average molecular weights are used in the polymerization process as a Group 4 transition metal catalyst, for example, first and second transition metal compounds of Formulas (1) and ( ₂ ), which are described below, belonging to the metallocene family, and hydrogen Based elastic copolymer having a weight average molecular weight of 100,000 or more is characterized in that it flows at room temperature as compared with a solid phase at room temperature.

In addition, since the Group 4 transition metal catalyst exhibits excellent activity, it is possible to produce the ternary elastomeric copolymer of the above embodiment even when using a relatively small amount compared to the Ziegler-Natta catalyst, and the ternary elastomeric copolymer, For example, EPDM rubbers can exhibit excellent transparency with less metal residues.

In the ternary elastomeric copolymer of one embodiment, the absorbance measured by a colorimeter may be about -5 to +5. The absorbance value was measured using LabScan XE manufactured by HunterLab. From this, it can be confirmed that the ternary elastomeric copolymer is transparent.

In addition, the ternary elastomeric copolymer of one embodiment may have a viscosity of about 10 to 20,000 cps or about 100 to 15,000 cps at room temperature. The viscosity was measured at room temperature using a Brookfield viscometer. From the viscosity value, it can be confirmed that the ternary elastomeric copolymer is in a liquid state. Such liquid three-component elastomeric copolymers have a property of flowing at room temperature and are capable of cross-linking sulfur / peroxide through compounding with other compounds. Accordingly, the present invention can be used in the fields of OLED encapsulants and adhesive materials, which have been difficult to apply to conventional solid-state elastic copolymers prepared using metallocene compounds.

In addition, since the ternary elastomeric copolymer has a narrow molecular weight distribution of about 1 to 4, or about 1 to 3, it can exhibit high transparency.

The copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene is a copolymer of 20 to 80% by weight of ethylene, 15 to 75% by weight of an alpha olefin having 3 to 20 carbon atoms and 0.5 to 20% Lt; / RTI > Such a copolymer can be produced by continuously feeding a monomer composition comprising 20 to 80% by weight of ethylene, 15 to 75% by weight of an alpha olefin having 3 to 20 carbon atoms and 0.5 to 20% by weight of a diene in the presence of a catalyst composition . In particular, as each monomer is contained in the above ratio, it can exhibit more excellent elasticity and flexibility.

In the ternary elastomeric copolymer of one embodiment, examples of the alpha olefin include propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, Heptadecene, 1-heptadecene, 1-nonadecene, 1-nonadecene, 1-undecene, 1-tridecene, 1-decene, 1-methyl-1-decene, 1-decene, 1-decene, 1-methylene-1-decene, Propylene, 1-butene, 1-hexene or 1-octene may suitably be used.

As the diene, a nonconjugated diene-based monomer may be used. Specific examples thereof include 5-1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12- Methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 3-methyl- Heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, Methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5-ethyl-1,4-pentadiene, 1,5-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, Hexadiene, 6-methyl-1,6-octadiene, 6-methyl-1,6-octadiene, Methylidene-2-norbornene, 5-methylene-2-norbornene, 5- (2- Propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (2,3- Pentenyl) -2-norbornene, 5- (3-methyl-hexenyl) 5- (2-methyl-6-heptenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl-4-pentenyl) Norbornene, 5-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-butylidene- , 3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. One or more dienes may be used.

Among these dienes, particularly, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, or 4-hexadiene is suitably used to obtain a three- Coalescence can be produced. On the other hand, 5-vinyl-2-norbornene (VNB) or dicyclopentadiene (DCPD) used as the diene in the preparation of the conventional three-component elastomer includes two double bonds, There is a limitation in that gel particles are formed in the polymerization process, the molecular weight of the copolymer is difficult to control, and the polymerization reaction is also difficult to control since it exhibits a crosslinked polymer structure.

According to another embodiment of the present invention, there is provided a process for producing a three-component elastomeric copolymer of one embodiment described above. The process for producing such a copolymer comprises reacting a catalyst composition comprising a first transition metal compound represented by the following formula (1) and a second transition metal compound represented by the following formula ( ₂ ) and hydrogen (H ₂ ) gas of 1 bar to 40 bar, Copolymerizing a monomer composition comprising 20 to 80% by weight of ethylene, 15 to 75% by weight of an alpha olefin having 3 to 20 carbon atoms and 0.5 to 20% by weight of a diene,

[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,

R ₁ to R ₁₃ 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; Two adjacent two of R ₁ to R ₁₃ may be connected to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form an aliphatic ring or an aromatic ring ;

M is a Group 4 transition metal;

Q ₁ and Q _{2, which} may be the same or different, 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.

Or about 30 to 50 wt.% Ethylene, about 15 to 75 wt.%, Or about 30 to 60 wt.% Ethylene, as determined by the following examples and the like. By weight of an alpha olefin having 3 to 20 carbon atoms and about 0.5 to 20% by weight, or about 5 to 15% by weight of a diene, with each monomer being reacted with a transition metal catalyst of the above formula (1) or ( ₂ ) It was confirmed that the ternary elastomeric copolymer of one embodiment having the aforementioned small molecular weight range and excellent transparency can be obtained with high yield and productivity.

This can be mainly due to the excellent catalytic activity and comonomer reactivity of the two specific catalysts. The specific catalysts of the first and second transition metal compounds exhibit excellent catalytic activity as a transition metal of Group 4, and can exhibit excellent selectivity and copolymerization reactivity with respect to comonomers such as alpha olefins and dienes. Furthermore, by using these two specific catalysts, the copolymer can be distributed while uniformly distributing the dienes in the polymer chain with a relatively high content. This is because the specific catalysts of the above formulas (1) and (2) are stably maintained in a quasi-ringing and hexagonal ring structure around the metal sites by the quinoline amido group and structurally easy to access the monomers .

Moreover, the ternary elastomeric copolymer uses two kinds of specific catalysts of the first and second transition metal compounds, and undergoes polymerization under hydrogen gas, and thus has a characteristic of being excellent in transparency while having a low molecular weight .

At this time, the hydrogen gas activates the inactive sites of the transition metal compound and causes a chain transfer reaction to control the molecular weight. Since the first and second transition metal compounds are excellent in hydrogen reactivity, a copolymer having a desired molecular weight and molecular weight distribution can be effectively obtained by controlling the amount of hydrogen gas used in the polymerization step.

The hydrogen gas may be introduced to be between about 1 bar and 40 bar, preferably between about 1 bar and 10 bar. The molecular weight of the copolymer to be produced can be controlled within a desired range by controlling the amount of the hydrogen gas used while exhibiting sufficient catalytic activity and thus a ternary elastomeric copolymer having appropriate physical properties depending on the application can be prepared.

As a result, it is possible to produce a ternary elastomeric copolymer having a low molecular weight of about 100,000 or less, with each monomer being homogeneously alternately distributed, with high productivity and yield.

However, in the case where the above-mentioned two kinds of specific catalysts are not used, only one of these catalysts is used, or when the content of each monomer is out of the appropriate content range, particularly the content of diene, when hydrogen gas is not used The resulting ternary elastomeric copolymer may not meet the low molecular weight range of an embodiment, the range of the transparency value, and the like.

On the other hand, in the method for producing a ternary elastomeric copolymer of another embodiment described above, the first and second transition metal compounds represented by the general formulas (1) and (2) will be described in more detail as follows.

First, hydrocarbyl in Formulas 1 and 2 may refer to a monovalent functional group in which a hydrogen atom is removed from a hydrocarbons. For example, an alkyl group such as ethyl, an aryl group such as phenyl, can do.

In the formulas (1) and (2), the metalloid is an element which is a metalloid and shows intermediate properties between metal and nonmetal, and may be, for example, arsenic, boron, silicon or tellurium. The M may be, for example, a Group 4 transition metal element such as titanium, zirconium or hafnium.

Among these first and second transition metal compounds, at least one compound selected from the group consisting of compounds represented by the following formulas can be suitably used as the first transition metal compound represented by the general formula (1)

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.

As the second transition metal compound represented by the above formula (2), at least one compound selected from the group consisting of compounds represented by the following formulas can be suitably used:

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.

Meanwhile, the catalyst composition used in the production method of another embodiment may further include at least one cocatalyst compound selected from the group consisting of the following chemical formulas (3), (4) and (5) in addition to the first and second transition metal compounds have:

(3)

- [Al (R) -O] _n -

In Formula 3,

R 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 4]

D (R) ₃

In Formula 4, R is as defined in Formula 3; D is aluminum or boron;

[Chemical Formula 5]

[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-

In Formula 5, 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 .

In such a promoter compound, examples of the compound represented by the general formula (3) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane.

Examples of the compound represented by the general formula (4) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- But are not limited to, cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, Trimethylboron, triethylboron, triisobutylboron, tripropylboron or tributylboron. Of these, trimethylaluminum, triethylaluminum or triisobutylaluminum can be suitably used.

The compound represented by the general formula (5) includes a non-coordinating anion which is compatible with a cation which is a Bronsted acid. Suitable anions are relatively large in size and contain a single coordination complex containing a metalloid. Particularly, compounds containing a single boron atom in the anion moiety are widely used. From this viewpoint, as the compound represented by the general formula (5), an anion-containing salt containing a coordination complex containing a single boron atom can be suitably used.

As specific examples of such compounds, there may be mentioned trialkylammonium salts such as trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate (Pentafluorophenyl) borate, tri (2-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, N, N-dimethylanilinium benzyltris (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (t-butyldimethylsilyl) -2,3,5,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (4-triisopropylsilyl) -2,3,5,6-tetra Fluorophenyl) borate, N, N-dimethylanilinium N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (pentafluorophenyl) borate, (2,3,4,6-tetrafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) Ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, Anilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-dimethyl-2,4,6-trimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) ) Borey , Pentyldimethylammonium tetrakis (pentafluorophenyl) borate, dodecyldimethylammonium tetrakis (pentafluorophenyl) borate, tetradecyldimethylammonium tetrakis (pentafluorophenyl) borate, hexadecyldimethylammonium tetrakis Octadecyldimethylammonium tetrakis (pentafluorophenyl) borate, eicosyldimethylammonium tetrakis (pentafluorophenyl) borate, methyldecylammonium tetrakis (pentafluorophenyl) borate, methyldido (Pentafluorophenyl) borate, methyldiotetradecylammonium tetrakis (pentafluorophenyl) borate, methyldihexadecylammonium tetrakis (pentafluorophenyl) borate, methyl dioctadecylammonium tetrakis Pentafluorophenyl) borate, methyldiacosylammonium tetrakis (pentafluoro (Pentafluorophenyl) borate, tridecylammonium tetrakis (pentafluorophenyl) borate, tridodecylammonium tetrakis (pentafluorophenyl) borate, trityl tetradecylammonium tetrakis (N-butyl) ammonium tetrakis (pentafluorophenyl) borate, trioctadecylammonium tetrakis (pentafluorophenyl) borate, trieocosyl ammonium tetrakis (pentafluorophenyl) (Pentafluorophenyl) borate, dodecyldi (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, octadecyldi (n-butyl) ammonium tetrakis (Pentafluorophenyl) borate or methyldi (dodecyl) ammonium tetrakis (pentafluorophenyl) borate, N-methyl-N-dodecyl anilinium tetrakis (Pentafluorophenyl) borate, and the like.

In the case of dialkylammonium salts, di- (i-propyl) ammonium tetrakis (pentafluorophenyl) borate or dicyclohexylammonium tetrakis (pentafluorophenyl) borate and the like can be mentioned.

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

On the other hand, in the above-mentioned method for producing a ternary elastomeric copolymer, the catalyst composition comprising the above-described first and second transition metal compounds and optionally a co-catalyst compound is obtained, for example, Contacting the compound with the promoter compound of Formula 3 or Formula 4 to obtain a mixture; And adding the promoter compound of Formula 5 to the mixture.

In the catalyst composition, the molar ratio of the first transition metal compound: the second transition metal compound may be about 10: 1 to 1:10, and the total transition metal compound : The molar ratio of the promoter compound of Formula 3 or Formula 4 may be from about 1: 5 to 1: 500, and the molar ratio of the total transition metal compound to the promoter compound of Formula 5 is about 1: 1 to 1: 10 < / RTI >

In addition, in the process for producing the ternary elastomeric copolymer, the catalyst composition may further comprise a reaction solvent, and examples of the reaction solvent include hydrocarbon solvents such as pentane, hexane or heptane; Aromatic solvents such as benzene or toluene, but are not limited thereto.

As already mentioned above, the alpha-olefins contained in the monomer composition include propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, -Heptene, 1-decene, 1-undecene, 1-dodecene and the like can be used. As the diene, a nonconjugated diene monomer can be used. Of these, monomers commonly used in the production of EPDM rubber, for example, propylene as the alpha olefin and 5-ethylidene-2-norbornene, 1,4-hexadiene or dicyclopentadiene as the diene Nonconjugated dienic monomer can be suitably used.

And, in the above-described method of producing a copolymer of another embodiment, the copolymerization step may be carried out at a temperature of about 100 to 170, or a temperature of about 100 to 160. When the copolymerization temperature is too low, it may be difficult to synthesize a ternary elastomeric copolymer in which three kinds of monomers are homogeneously alternately distributed. If the polymerization reaction temperature is too high, the monomer or the produced copolymer may be thermally decomposed. In addition, such copolymerization can proceed by a solution polymerization method. At this time, the above-described catalyst composition can be used in the form of a homogeneous catalyst dissolved in such a solution.

For the progress of the solution polymerization, the copolymerization step may be carried out while supplying the catalyst composition containing the above-mentioned monomer composition, the first and second transition metal compounds and optionally the cocatalyst to the reactor in a solution state.

The ternary elastomeric copolymer obtained according to the present invention can overcome the limitations of the previously known metallocene type transition metal catalyst such as EPDM rubber and can satisfy excellent transparency with other physical properties, It can be very advantageously used as a liquid EPDM rubber while taking advantage of the advantages inherent in the catalyst.

1 is a graph showing the results of GPC analysis of the ternary elastomeric copolymer prepared in the examples.
2 is a graph showing the results of GPC analysis of the ternary elastomeric copolymer of Comparative Example.
3 is a photograph for color comparison of the ternary elastomeric copolymers of Example 1 and Comparative Example 1. Fig.

≪ Synthesis of ligand and transition metal compound >

All ligands and catalyst synthesis were carried out using standard Schlenk and Blove-box techniques under a nitrogen atmosphere to block the contact of air and moisture. Organic solvents used in the reaction were purified by standard methods and used Respectively. The synthesized ligand and catalyst structure were confirmed using a 400 MHz nuclear magnetic resonance (NMR) and X-ray spectroscopy.

Examples of the first and second transition metal compounds in the following examples are [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kepa-N] titanium dimethyl ([(1,2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kapa-N] titanium dimethyl and [(2-methylindolin-7-yl) tetramethylcyclopentadienyl- (2-methylindolin-7-yl) tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl was used as the cocatalyst compound and N, N-dimethylanilinium tetrakis Phenyl) borate and triisobutyl aluminum were used. The first and second transition metal compounds were prepared and used in the same manner as in Examples 2 and 14 of Korean Patent No. 0,976,131, and the co-catalyst compound was used in the same manner as in Example 9 of Korean Patent No. 0,820,542 A co-catalyst compound was prepared and used.

< Example  1 to 3> ethylene, propylene and 5- Ethylidene -2- Nobonen Triplet  Preparation of elastic copolymer

After injecting 440 g of hexane solvent into a 2 L pressure reactor, 0.7 mL of triisobutylaluminum was added to the reactor. Thereafter, the reactor was operated at 500 rpm for 3 minutes, readjusted to 0 rpm, and then a certain amount of hydrogen gas was introduced. 58 g of propylene was then charged and the reactor was preheated to 120 DEG C while stirring at 500 rpm. After the temperature stabilized, the reactor was charged with ethylene and maintained at 24 bar. Ethylidene-2-norbornene in a state of sufficiently saturated ethylene gas in the reactor, and a solution in which the above-mentioned N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved as a co-catalyst compound , N-hexane containing triisobutylaluminum, and the first and second transition metal compounds include [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-etha 5 Tetramethylcyclopentadienyl-eta5, kapa-N] titanium dimethyl and [(2-methylindolin-7-yl) tetramethyl ([(2-Methylindolin-7-yl) tetramethylcyclopentadienyl-eta 5, kapa-N] titanium dimethyl was dissolved in hexane and the mixture was stirred at 500 rpm Lt; / RTI &gt; for 10 minutes.

After completion of the reaction, the ethylene gas was shut off to remove the residual gas in the reactor, and then excess ethanol was added to the copolymer solution obtained by the reaction to precipitate the copolymer. The obtained copolymer was washed with ethanol for 2 to 3 times, the solvent was removed, and the resulting solution was dried under reduced pressure at 60 캜 in a vacuum oven to prepare a ternary elastomeric copolymer of Example 1. The ternary copolymers of Examples 2 to 3 were prepared in the same manner as in Example 1, except that the conditions (ethylene gas supply pressure and propylene feed rate) shown in Table 1 below were changed. The content of each monomer in the thus-obtained copolymer is as shown in Table 1 below, and the copolymer of Example 1 exhibits a transparent color.

< Comparative Example  1 to 2> Commercial ethylene, propylene and 5- Ethylidene -2- Nobonen Triplet  Elastic copolymer

Trilene-65 and Trilene-67 of Lion copolymer, a commercially available EPDM rubber known as a metallocene catalyst, were used as the elastic copolymers of Comparative Examples 1 and 2, respectively. The content of monomers in each copolymer is as shown in Table 1 below, and as shown in FIG. 3, Comparative Examples 1 and 2 showed pale yellow hue.

H ₂ gas Ethylene
gas PP
flow ENB
flow Ethylene
content PP content ENB
content (bar) (bar) (g) (g) (weight%) (weight%) (weight%) Example 1 2 24 58 6 40.4 50.2 9.4 Example 2 One 24 58 6 44.8 46.3 8.9 Example 3 2 24 58 12 44.1 42.2 13.8 Comparative Example 1 39.2 49.5 11.3 Comparative Example 2 38.4 51.7 10.0

PP: propylene

ENB: 5-ethylidene-2-norbornene

< Experimental Example >

The ternary elastomeric copolymers of Examples and Comparative Examples were measured for physical properties by the following methods and are summarized in Table 2.

(1) Method of measuring weight average molecular weight

Using PL-GPC 220 manufactured by Polymer Laboratory equipped with three linear mixed bed columns, 1,2,4-trichlorobenzene was used as a solvent at a temperature of 160 ° C at a flow rate of 1.0 ml / min.

(2) Viscosity measurement method

And measured at room temperature using a Brookfield rotary viscometer.

(3) Method of measuring absorbance

About 20 g of the ternary elastomeric copolymers of the above examples and comparative examples were placed in a measurement container, and placed in a measuring container at room temperature for 3 hours to remove bubbles. Then, absorbance was measured using LabScan XE manufactured by HunterLab.

MW PDI Viscosity Absorbance (kg / mol) (cps) Example 1 45.1 2.90 10800 +3 Example 2 59.2 2.27 13200 +2 Example 3 36.6 1.99 9800 +3 Comparative Example 1 44.5 2.86 15600 +16 Comparative Example 2 57.8 2.98 14200 +14

Claims (9)

As the copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene obtained in the presence of a transition metal catalyst,
i) a weight average molecular weight measured by GPC of from 10,000 to 100,000,
ii) a ternary elastomeric copolymer having an absorbance of -5 to +5 as measured by a colorimeter.
The composition according to claim 1, wherein the copolymer of ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene comprises 20 to 80% by weight of ethylene, 15 to 75% by weight of an alpha olefin having 3 to 20 carbon atoms, and 0.5 to 20% A copolymer of dienes, and a ternary elastomeric copolymer.
The ternary elastomeric copolymer according to claim 1, having a viscosity of 10 to 20,000 cps.
The ternary elastomeric copolymer according to claim 1, having a molecular weight distribution of 1 to 4.
The process according to claim 1, wherein the alpha olefin is at least one selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene and the diene is at least one selected from the group consisting of 5-ethylidene- Norbornene and 4-hexadiene, wherein the ternary elastomeric copolymer is at least one selected from the group consisting of norbornene and 4-hexadiene.
To the under first transition metal compound and to hydrogen (H ₂₎ gas of the catalyst composition, and 1 bar to 40 bar and a second transition metal compound represented by the formula (2) represented by the general formula (1), 20 to 80% by weight ethylene , 15 to 75% by weight of an alpha olefin having 3 to 20 carbon atoms and 0.5 to 20% by weight of a diene.
[Chemical Formula 1]

(2)

In the above Formulas 1 and 2,
R ₁ to R ₁₃ 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; Two adjacent two of R ₁ to R ₁₃ may be connected to each other by an alkylidene radical containing an alkyl group having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms to form an aliphatic ring or an aromatic ring ;
M is a Group 4 transition metal;
Q ₁ and Q _{2, which} may be the same or different, 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.
7. The method of claim 6, wherein the first transition metal compound is at least one selected from the group consisting of compounds represented by the following formulas:

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.
The method for producing a ternary elastomeric copolymer according to claim 6, wherein the second transition metal compound is at least one selected from the group consisting of compounds represented by the following formulas:

R ₂ and R ₃ may be the same or different from each other and are each independently hydrogen or a methyl radical, M is a Group 4 transition metal, Q ₁ and Q ₂ may be the same or different from each other and each independently methyl A radical, a dimethylimido radical or a chlorine radical.
7. The method of claim 6, wherein the catalyst composition further comprises at least one promoter compound selected from the group consisting of the following chemical formulas (3), (4) and (5)
(3)
- [Al (R) -O] _n -
In Formula 3,
R 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 4]
D (R) ₃
In Formula 4, R is as defined in Formula 3; D is aluminum or boron;
[Chemical Formula 5]
[LH] ⁺ [ZA ₄ ] ^- or [L] ⁺ [ZA ₄ ] ^-
In Formula 5, 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 .

Images