KR20150126585A - Preparation method of elastic terpolymer - Google Patents

Abstract

The present invention relates to a method for producing an ethylene/alpha-olefin/diene elastic copolymer having a high viscosity and high molecular weight, in which the energy efficiency of the entire process is optimized. The method for producing an elastic copolymer comprises the steps of: copolymerizing an ethylene/alpha-olefin/diene elastic copolymer; and separating and removing the solvent and unreacted monomers from the polymer solution and recovering the elastic copolymer, by sequentially using a gas-liquid separator and a stripper in the purification of the solvent and unreacted monomers.

Description

TECHNICAL FIELD [0001] The present invention relates to a three-component elastomeric copolymer,

The present invention relates to a process for recovering a high-viscosity and high-molecular-weight elastomer by optimizing energy efficiency by successively using a gas-liquid separator and a stripper in a process of copolymerizing an ethylene /? - olefin / diene monomer and purifying a solvent and an unreacted monomer from a polymer solution Based elastomeric copolymer comprising the steps of:

In general, when an ethylene-propylene-diene-monomer (hereinafter referred to as EPDM) is produced by using a vanadium catalyst, a polymer polymer is prepared by using an aqueous solution of NaOH and high-pressure steam to remove Cl contained in the catalyst from the polymer composition. Is removed. However, this method has a complicated process because the catalyst in the polymer polymer is troublesome to remove.

Also, in the process of producing EPDM using a vanadium catalyst, high energy is consumed by removing high-pressure steam directly into the polymer solution in order to recover unreacted monomers, comonomers and solvent. In addition, unreacted monomers and comonomers and solvents removed from the polymer composition all require a lot of refining costs since they are completely recycled to the reactor by removing water and the like through further purification. For example, in order to produce 10 tons of EPDM polymer per hour, the amount of monomers and comonomer hexane excluding EPDM polymer is 50 to 100 tons at the outlet of the reactor. In order to separate the polymer from the polymer and reuse it in the reactor, And catalytic poison components such as catalyst killing agents must be removed. However, the conventional method has a problem of inefficiency due to excessive energy cost during this process.

In addition, in order to recover the polymer in the EPDM production method using the vanadium catalyst composition, the solvent and unreacted monomers are recovered by steam stripping. Korean Patent Registration No. 10-0226175 describes a method for removing vanadium catalyst composition by using water or an aqueous alkali solution to remove catalyst residues. U.S. Pat. No. 3,590,026 also removes the solvent and unreacted monomers through a two-step steam-stripping process. However, when the solvent and unreacted monomers are removed from the polymer solution through the steam-stripping, the energy consumption is twice as large as that of the present invention, which is described later.

In order to overcome such a problem, Korean Patent Registration No. 10-0496101 discloses a method for recovering a polymer by sequentially passing through an anhydrous solvent recovery step in the second step in the process for producing EPDM using a metallocene catalyst composition. Although this method has advantages of using less energy, the flow of the polymer solution is not good when a high viscosity and high molecular weight EPDM polymer is produced. In addition, when a devolatilizing extruder is used, a polymer having a high density is produced and blended with oil, carbon black, accelerator, etc. for compounding. That is, the process can not produce high molecular weight EPDM, and after the purification, the extruder is too high in shear to produce a product properly.

Therefore, there is a continuing need to develop a process for producing an EPDM elastic copolymer capable of producing a high molecular weight EPDM and capable of improving productivity and energy efficiency.

The present invention provides a process for producing a ternary elastomeric copolymer capable of producing a high molecular weight ethylene-alpha olefin-diene-based elastic copolymer without increasing the shear rate of the extruder while enhancing energy efficiency.

The present invention also provides a process for producing an ethylene-alpha olefin-diene-based elastic copolymer with improved productivity.

The present invention relates to a process for the preparation of a monomer composition comprising, in the presence of a metallocene catalyst and a solvent, a monomer composition comprising from 40 to 70% by weight of ethylene, from 15 to 55% by weight of alpha olefins of from 3 to 20 carbon atoms and from 0.5 to 20% Copolymerizing in a reactor to produce a polymer solution comprising an ethylene-alpha olefin-diene based copolymer; And

Separating the solvent and the unreacted monomer from the polymer solution using a gas-liquid separator and a stripper in sequence, and recovering the ethylene-alpha olefin-diene copolymer,

Wherein the gas-liquid separator includes a step of removing the solvent and the unreacted monomer from the polymer solution at a temperature of the upper portion of the gas-liquid separator at a temperature of 150 to 160 DEG C and a pressure of 5 to 10 bar,

Wherein the stripper includes a step of adding water vapor as a carrier gas under a condition of a temperature of 140 to 180 ° C and a pressure of 4 to 10 bar to remove remaining solvent and unreacted monolayer from the polymer solution passed through the gas-

Wherein the metallocene catalyst comprises 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).

[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.

The gas-liquid separator separates and removes 40 to 70% by weight of the total amount of all substances except for the total polymer contained in the polymer solution. In the stripper, residual amount of the remaining substance except for the polymer contained in the polymer solution, And separating and removing unreacted monomers.

In the stripper, the solvent contained in the copolymer and the unreacted monomer may be recovered to be within 10 wt% of the total copolymer content.

According to the present invention, the content of the ethylene-alpha olefin-diene copolymer contained in the polymer solution before passing through the gas-liquid separator is 10 to 20% by weight, and the content of the ethylene-alpha olefin-diene copolymer Based copolymer may be from 20 to 50% by weight.

The solvent and unreacted monomers separated in the gas-liquid separator and the stripper can be reused for the copolymerization of ethylene-alpha olefin-diene.

And further comprising the step of preparing the copolymer in the form of a bale or a pellet after the step of recovering the copolymer.

The catalyst composition may further comprise at least one cocatalyst 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 .

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-2-norbornene, 5- Vinyl-2-norbornene, 1,4-hexadiene, and dicyclopentadiene.

As described above, according to the present invention, since the solvent and the unreacted monomer are removed from the polymer solution sequentially by using the gas-liquid separator (flashing process) and the stripper in the process of producing the ethylene-alpha olefin-diene elastic copolymer, A high molecular weight elastic copolymer can be obtained. In addition, since the solvent and unreacted monomers recovered from the polymer solution can be recovered and used for copolymerization for preparing the elastomer, the present invention can appropriately prepare a high molecular weight EPDM without shear of the extruder while improving energy efficiency .

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a solution polymerization process for producing a general EPDM elastic copolymer.
2 is a schematic view illustrating a process of recovering a solvent and an unreacted monomer sequentially using a gas-liquid separator and a stripper in the process of producing an EPDM elastic copolymer according to the present invention.
3 is a schematic view illustrating an apparatus for producing an EPDM elastic copolymer having a gas-liquid separator and a stripper according to the present invention.

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

As used herein, the term "ternary elastomeric copolymer" means any elastic copolymer in which three kinds of monomers such as ethylene, an alpha olefin having 3 to 20 carbon atoms and a diene are copolymerized (for example, Coalescence). 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, there is provided a polyolefin composition comprising, in the presence of a metallocene catalyst and a solvent, 40 to 70% by weight of ethylene, 20 to 50% by weight of an alpha olefin having 3 to 20 carbon atoms and 0 to 20% Copolymerizing the monomer composition in a polymerization reactor to prepare a polymer solution containing an ethylene-alpha olefin-diene-based copolymer; And separating the solvent and the unreacted monomer from the polymer solution using a gas-liquid separator and a stripper in sequence, and recovering the ethylene-alpha olefin-diene-based copolymer. do.

The present invention is characterized in that a gas-liquid separator and a stripper are sequentially used for recovering a solvent and unreacted monomers from a polymer solution obtained after the reaction in the process of producing an ethylene-alpha olefin-polyene elastomer such as EPDM.

More specifically, the present invention is characterized in that the solvent and the unreacted monomer are primarily recovered from the polymer solution through the gas-liquid separator to reduce the energy cost. In the present invention, a stripper is sequentially disposed behind the gas-liquid separator to recover a residual solvent in the polymer solution and unreacted monomers by steam stripping to obtain a copolymer having a high viscosity and a high molecular weight. Therefore, the polymer produced according to the present invention exhibits properties that are easy to commercialize because of excellent bonding with additives.

The present invention also relates to a process for efficiently separating and recovering a solvent, an unreacted monomer and a comonomer from an elastomeric polymer containing EPDM in a polymer solution produced in a single polymerization reactor to produce a polymer, removing the catalyst poisoning material, Can be provided. According to this process, the present invention can reuse the solvent and the unreacted monomer separated in the gas-liquid separator and the stripper in the copolymerization reaction for producing the ethylene-alpha olefin-diene elastic copolymer.

The gas-liquid separator separates and removes 40 to 70% by weight of the total amount of all materials except the entire polymer contained in the polymer solution. In the stripper, residual solvent of the remaining materials except the polymer contained in the polymer solution, And separating and removing the reactive monomer.

In the stripper, the solvent contained in the copolymer and the unreacted monomer may be recovered to be within 10 wt% of the total copolymer content.

According to the present invention, the content of the ethylene-alpha olefin-diene copolymer contained in the polymer solution before passing through the gas-liquid separator is 10 to 20% by weight, and the content of the ethylene-alpha olefin-diene copolymer Based copolymer may be from 20 to 50% by weight. That is, the content of the elastic copolymer before purification is 10 to 20% by weight, and the content of the elastic copolymer after being subjected to the gas-liquid separator is about 20 to 50% by weight. . Also, in the present invention, both the solvent and the unreacted monomer as well as the comonomer are removed together through the second stripper, thereby improving the viscosity and the molecular weight of the final polymer.

In particular, in the present invention, a solvent and unreacted monomers, comonomers, and the like can be effectively removed from the polymer solution by using a gas-liquid separator and a stripper.

Preferably, the gas-liquid separator may include a step of removing the solvent and unreacted monomers from the polymer solution at a temperature of the upper portion of the gas-liquid separator at a temperature of 150 to 160 ° C and a pressure of 5 to 10 bar. If the temperature of the upper portion of the gas-liquid separator is lower than 150 ° C or the pressure exceeds 10 bar, there is a problem that the solvent and unreacted monomers are not removed from the polymer solution by a desired amount. In addition, if the temperature exceeds 160 ° C or below 5 bar, there is a problem that the solvent and the unreacted monomer are removed from the polymer solution more than the desired amount. The gas-liquid separator means a gas-liquid anhydrous separator.

The stripper may further include a step of removing the residual solvent and the unreacted monolayer from the polymer solution that has been subjected to the gas-liquid separator by adding steam to the carrier gas under the conditions of a temperature of 90 to 120 ° C and a pressure of 0.3 to 3 bar. At this time, when the temperature of the stripper is less than 90 ° C or more than 0.3 bar, the solvent and the unreacted monomer are not removed from the polymer solution by a desired amount. In addition, if the temperature exceeds 180 DEG C or less than 3 bar, there is a problem that excess steam is consumed to remove the solvent and unreacted monomers from the polymer solution.

In addition, the process for preparing an elastomeric copolymer according to one embodiment of the present invention comprises the step of adding a certain amount of monomer, i.e., about 40-70 wt%, or about 50-70 wt% ethylene, about 15-55 wt% Or about 25 to 45% by weight of an alpha olefin having 3 to 20 carbon atoms and about 0.5 to 20% by weight, or about 2 to 10% by weight of a diene.

According to the present invention, it is possible to copolymerize each of these monomers in the presence of a catalyst composition containing a Group 4 transition metal to prepare an ethylene-alpha olefin-diene-based elastic copolymer. Such copolymerization can be carried out by solution polymerization, in particular, continuous solution polymerization. At this time, the above-described catalyst composition can be used in the form of a homogeneous catalyst dissolved in such a solution.

After the copolymerization, the above-described gas-liquid separator and the stripper are sequentially used. Thus, the polymer solution is purified to obtain a three-dimensional elastomeric copolymer of one embodiment satisfying a large molecular weight range and an ethylene content, .

Also, the method for producing the elastic copolymer is a method of polymerizing at a reaction temperature of 80 to 150 ° C and a reaction pressure of 75 to 120 bar for a retention time of 0.05 to 0.5 hours by solution polymerization to obtain an ethylene copolymer having a polymer concentration of 5 to 20% - alpha olefin-diene elastomeric copolymer. According to the present invention, as the content of each monomer is adjusted to the optimized range as described above, the distribution of each monomer in the polymer chain can be arranged more uniformly, Thereby enabling effective manufacture of the copolymer.

The method of the present invention may further comprise the step of preparing the copolymer in the form of a bale or a pellet after the step of recovering the copolymer. Methods for commercialization in the form of bale or pellet may be accomplished by methods well known in the art.

In the method for producing an ethylene-alpha olefin-diene elastic copolymer according to one embodiment of the present invention, a method for producing an EPDM elastic copolymer will be described with reference to the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of a solution polymerization process for producing a general EPDM elastic copolymer. As shown in Figure 1, the EPDM manufacturing process is largely divided into a first zone of solvent / raw material purification, a second zone of polymer preparation, a third zone separating solvent / unreacted monomers and a fourth zone of veil / pellet preparation Can be divided.

The first region is a region for purifying a solvent and an unreacted monomer or the like separated from the polymer after being used for producing the raw material and the polymer. The first region includes a raw material for producing an elastomer and a portion to which a solvent is supplied, and may be purified to remove impurities.

The second region is a region where the polymer is produced in the presence of the metallocene catalyst composition using the purified raw material and the solvent in the first region. Thus, the metallocene catalyst may be supplied to the second region.

The third region is a step of separating the solvent and the unreacted monomer from the polymer solution prepared in the second region and sending the polymer to the fourth region.

The fourth region generally further comprises separating residual solvent and unreacted monomer not separated in the third region from the polymer separated in the third region, removing water and the like, and then commercializing the remaining solvent. In addition, the fourth region is an area for producing a product in the form of pellets or bale.

However, in the case of the conventional method, since the residual solvent and the unreacted monomer must be separated from each other in the course of commercializing the polymer, the energy efficiency is lowered and there is a limit in producing an elastomer having a high viscosity and a high molecular weight.

On the other hand, in the present invention, as shown in FIG. 2, the step of using the gas-liquid separator and the stripper in the third region completely separates the solvent and the unreacted monomer from the polymer solution and collects the recovered monomer. That is, FIG. 2 schematically shows a process of recovering a solvent and an unreacted monomer sequentially using a gas-liquid separator and a stripper in the process of producing an EPDM elastic copolymer according to the present invention.

At this time, the gas-liquid separator refers to the anhydrous gas-liquid separator shown in FIG. 2, and the stripper refers to a steam stripper in which steam is supplied as a carrier gas.

According to this embodiment, in the course of the purification of the polymer solution, the solvent used in the reaction, the unreacted monomers and the comonomer are separated when the anhydrous gas-liquid separator and the steam stripper are staged, and the separated solvent and unreacted monomers are recovered And then sent back to the first region to be subjected to a solvent / raw material refining process and reused in the process of producing the polymer of the second region.

Further, in the present invention, the structures of the first region, the second region and the fourth region may be performed according to a method well known in the art, except that the gas-liquid separator and the stripper are used stepwise in the third region.

For example, the solvent / raw material refining process of the first region is not particularly limited, and all methods well known in the art for removing impurities can be used.

In the second region of the EPDM according to the present invention, the solution may be polymerized using the metallocene catalyst as described above.

In addition, the fourth zone can perform the commercialization of the polymer through a general process for the production of veils / pellets.

The elastic copolymer of the present invention according to one embodiment of the present invention is obtained by polymerizing ethylene, an alpha-olefin having 3 to 20 carbon atoms and a diene introduced from a raw material supply device in the presence of a metallocene catalyst and a solvent, A polymerization reactor for producing a polymer solution comprising: A gas-liquid separator connected to the polymerization reactor for primarily separating the solvent and the unreacted monomer from the polymer solution; A stripper for sequentially separating the remaining solvent and unreacted monomers from the polymer solution in which the solvent and the unreacted monomers are first separated from the gas-liquid separator, the stripper being connected to the gas-liquid separator sequentially and recovering the copolymer; And a dryer for drying the copolymer recovered from the stripper. In addition, since the method for producing an elastic copolymer of the present invention is produced using a metallocene catalyst, there is an advantage that a catalyst in a polymer polymer is not required to be removed.

The polymerization reactor may be equipped with a continuous stirring apparatus and may have an outlet through which the polymer solution containing the ethylene-propylene-diene copolymer can be transferred to the next step after solution polymerization is completed. The outlet may be located at the top of the side of the polymerization reactor, allowing the polymer solution to be continuously discharged during the polymerization process and be transported to the gas-liquid separator via a pump. Therefore, a pump may be provided between the polymerization reactor and the gas-liquid separator as means for transferring the polymer solution obtained from the polymerization reactor to the gas-liquid separator.

In addition, the gas-liquid separator may have an outlet for withdrawing and collecting the entire solvent and unreacted monomers from the polymer solution supplied from the polymerization reactor, at an upper portion of the gas-liquid separator. That is, the solvent and the unreacted monomer, which are separated and purified in the gas-liquid separator, may be recycled to the raw material supply unit through a transfer line connected to the upper portion of the gas-liquid separator.

In addition, the remaining polymer solution in the gas-liquid separator is discharged through a transfer line connected to the lower portion of the gas-liquid separator, and is moved to the stripper. In the stripper, the remaining amount of solvent and unreacted monomers and the like are purified from the first purified polymer solution in the gas-liquid separator. Means for supplying water vapor, which is a carrier gas, may be connected to the stripper, and control means for controlling the steam supply amount may be provided. In addition, the secondarily separated and purified solvent and unreacted monomers in the stripper can be recycled to the feedstock supply through the transfer line connected to the top of the stripper.

The polymer in which the residual solvent and the unreacted monomer have been removed through the secondary purification process in the stripper can be transferred to the dryer through the transfer line connected to the lower side of the stripper. The drying conditions of the polymer in the dryer are not particularly limited and can be performed under conditions well known in the art.

On the other hand, in the method for producing a ternary elastomeric copolymer of one embodiment, examples of the alpha olefin include propylene, 1-butene, 1-hexene, 1-octene, 1-pentene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 9-nonadecene, 1-heptadecene, -Methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc. Among these, alpha olefins of 3 to 10 carbon atoms, As typical examples, propylene, 1-butene, 1-hexene or 1-octene may be appropriately used. As the diene, a nonconjugated diene-based monomer may be used. Specific examples thereof include 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- 5- (4-pentenyl) -2-norbornene, 5- (1-methyl- (3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) Methyl-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) 5-hexenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) Norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl- Norbornene, 5-isopropylidene-2-norbornene, 5-butylidene-2-norbornene, 5-isobutylidene- Ethylidene-3-isopropylidene-5-nobo Norbornene, 2-propenyl-2,2-norbornadiene, 1,4-hexadiene or dicyclopentadiene, and one or more dienes selected from these may be used. Of these, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 1,4-hexadiene or dicyclopentadiene can be suitably used.

In addition, the metallocene catalyst used for preparing the elastic copolymer in the present invention may be prepared by using 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) .

[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.

In the general formulas (1) and (2), hydrocarbyl may denote a monovalent functional group in which a hydrogen atom is removed from a hydrocarbons. For example, an alkyl group such as ethyl or an aryl group such as phenyl may be encompassed have.

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.

In addition, the catalyst composition may further comprise at least one cocatalyst 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 .

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, the catalyst composition comprising the above-mentioned first and second transition metal compounds and optionally the co-catalyst compound can be produced, for example, by reacting the first and second transition metal compounds with the co- Contacting the compound 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 >

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.

The elastomeric copolymer prepared by the method of one embodiment of the present invention is a ternary elastomeric copolymer in which three kinds of monomers such as ethylene, alpha olefin and diene are copolymerized in a certain content range, and it is about 100,000 to 500,000, Or a relatively large weight average molecular weight of about 1500,000 to 400,000, or 200,000 to 300,000. This large weight average molecular weight is achieved due to the excellent activity of the first and second transition metal compounds of Formulas 1 and 2 described above belonging to a Group 4 transition metal catalyst, e. G., The metallocene family, As the ternary elastomeric copolymer has such a large molecular weight, the ternary elastomeric copolymer, for example, the EPDM rubber, can exhibit excellent mechanical properties.

Further, the ternary elastomeric copolymer of one embodiment according to the present invention can satisfy both excellent mechanical properties and improved elasticity and flexibility at the same time. Therefore, the ternary elastomeric copolymer of one embodiment can be produced with excellent productivity and yield peculiar to a Group 4 transition metal catalyst belonging to the metallocene series, for example, and is excellent in mechanical properties, The EPDM rubber produced by the metallocene-type transition metal catalyst of the prior art solves the problem of excellent elasticity and flexibility at the same time.

In addition, the elastic copolymer of one embodiment of the present invention obtained by such a method has a pattern viscosity (1 + 4 ai125 deg. C) range, for example, about 5 to 150, 130, or about 10 to 120, respectively.

Hereinafter, the present invention will be described in more detail in the following examples. It is to be understood, however, that the invention is not limited to the following examples.

[Examples 1 to 10]

As shown in FIG. 3, a polymerization reactor 1, a gas-liquid separator 2, a stripper 3 equipped with a charging device and a drier 4 ) Were sequentially installed in the same manner as in Example 1, to prepare an EPDM elastomer. 3 is a schematic view illustrating an apparatus for producing an EPDM elastic copolymer having a gas-liquid separator and a stripper according to the present invention.

Specifically, a composition comprising a raw material (ethylene (C 2 H 4), propylene (C 3 H 6) and 5-ethylidene-2-norbornene (ENB)) and a solvent (hexane) shown in Table 1 below the side surface of the polymerization reactor, Of the catalyst composition (metallocene catalyst) was continuously introduced.

That is, examples of the first and second transition metal compounds include the [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, kepa-N] [(2-methylindolin-7-yl) tetramethylcyclopentadienyl-eta 5, kepa-N] titaniumdimethyl dissolved in hexane was added to the reactor. As the co-catalyst compound, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was added to the reactor in the state of being dissolved in toluene. In addition, triisobutylaluminum as an additional promoter compound was added to the reactor in the state of being dissolved in hexane.

Further, continuous supply of each monomer and the catalyst composition proceeded, and continuous polymerization of the polymerization reactor was carried out so that solution polymerization proceeded. When the solution polymerization was completed, the polymer solution containing the ethylene-propylene-diene copolymer was continuously discharged from the upper side of the polymerization reactor 1 and transferred to the gas-liquid separator 2 through the pump. In addition, in the gas-liquid separator, some of the entire solvent and unreacted monomers were separated from the polymer solution, and then discharged through the upper part of the gas-liquid separator. In addition, the remaining polymer solution in the gas-liquid separator was discharged through the lower part of the gas-liquid separator and moved to the stripper 3. In the stripper 3, water vapor was continuously introduced as a carrier gas, and the remaining solvent and unreacted monomers were separated from the polymer solution passed through the gas-liquid separator. The residual solvent and the unreacted monomer separated from the polymer solution were discharged through the upper part of the stripper and recovered. The copolymer (EPDM elastic copolymer) after the residual solvent and the unreacted monomer were removed was discharged through the lower part of the stripper, (4). The copolymer was dried in the dryer (4) at a temperature of 100 DEG C for 4 hours, and recovered. The recovered copolymer was used for commercialization in the form of pellets by a conventional method. Also, the solvent discharged from the gas-liquid separator and the stripper, and the recovered solvent and the unreacted monomer were transferred to a raw material supply device and reused for the production of an ethylene-propylene-diene copolymer.

Table 2 shows conversion ratios and activity of the catalysts under the feedstock input conditions and the reactor internal conditions. The composition and the pattern viscosity (MV) of the EPDM elastic copolymer were measured, and the results are shown in Table 3. Table 4 shows the removal rates of the solvent and unreacted monomers in the whole process.

C2H4 C3H6 ENB C6H12 Catalyst ^{a )} Cocatalyst ^{b )} TiBal ^{c )} kg / hr kg / hr ml / min kg / kr ml / min ml / min ml / min Example 1 0.95 0.83 2.47 7.47 4.53 8.00 6.53 Example 2 0.90 0.82 3.50 7.00 5.00 8.00 7.00 Example 3 0.90 0.82 3.50 7.00 5.00 8.00 7.00 Example 4 0.89 0.55 5.13 6.68 5.00 5.00 5.00 Example 5 0.89 0.55 5.13 6.68 5.00 5.00 5.00 Example 6 0.90 0.45 3.40 6.81 5.00 5.00 3.00 Example 7 0.90 0.45 3.40 6.81 5.00 5.00 3.00 Example 8 0.89 0.55 5.13 6.68 4.00 5.00 5.00 Example 9 0.89 0.55 5.13 6.68 2.50 5.00 5.00 Example 10 0.89 0.55 1.51 7.68 3.50 3.50 3.00 week)
a) catalyst: first and second transition metal compounds (molar ratio 1: 1), 0.1 mmol / l
b) Co-catalyst: N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 0.5 mmol / l
c) Triisobutylaluminium (TiBal): 10 mmol / l

Feed R.TOP Press. Conversion Rate (%) activation ℃ ℃ kg / cm2 C2H4 C3H6 C6H12 Ton / mol.hr Example 1 -6.5 121.7 89 60.7 35.8 36.8 33.8 Example 2 15.8 120 89 63.4 42.8 41.5 33.3 Example 3 27.0 130 89 69.5 47.0 47.4 36.7 Example 4 10.2 152.4 89 91.0 60.0 58.0 43.3 Example 5 34.0 158.9 89 86.3 51.7 53.5 40.0 Example 6 20.3 159.6 89 99.0 61.4 61.7 42.7 Example 7 -3.8 148.1 89 92.3 62.9 64.0 41.0 Example 8 50.3 159 89 66.2 39.6 41.0 38.3 Example 9 50.8 158.1 89 63.9 38.3 39.6 59.2 Example 10 59.0 158.9 89 94.4 66.3 65.2 59.9

Furtherance MV Weight average molecular weight (Mw) C2H4 C3H6 C6H12 1 + 4, 125 DEG C Example 1 62.5 32.2 5.3 110.0 254,000 Example 2 57.1 35.1 7.8 132.5 369,000 Example 3 56.9 35.0 8.1 75.7 247,000 Example 4 62.3 25.4 12.3 72.9 288,000 Example 5 64.0 23.7 12.3 59.3 232,000 Example 6 69.6 21.6 8.8 65.3 240,000 Example 7 67.5 23.0 9.5 87.0 296,000 Example 8 64.0 23.7 12.3 55.2 224,000 Example 9 64.0 23.7 12.3 81.4 267,000 Example 10 66.8 29.0 4.2 33.4 154,000

From the results shown in Table 3, it can be seen that the present invention shows that a ternary elastomeric copolymer having a high viscosity is obtained when EPDM has a Mooney viscosity of 30 or more (1 + 4 a) 125 ° C.

Example Reaction outlet Gas-liquid separator Stripper Solvent and
Unreacted monomer
Removal rate Total flow Copolymer
content Monomer and solvent amount The amount of unreacted monomer and solvent Total flow after Flash Copolymer
content The amount of unreacted monomer and solvent Copolymer yield Gas-liquid separator Stripper kg / hr weight% kg / hr kg / hr kg / hr weight% kg / hr kg / hr weight% weight% One 10.13 9.1 9.21 4.80 5.33 17.3 4.41 0.92 52.1 47.9 2 9.70 10.3 8.70 4.35 5.35 18.7 4.35 1.00 50.0 50.0 3 9.70 11.3 8.60 4.70 5.00 22.0 3.90 1.10 54.7 45.3 4 8.99 14.5 7.69 4.15 4.84 26.9 3.54 1.30 54.0 46.0 5 8.99 13.3 7.79 4.95 4.04 29.7 2.84 1.20 63.6 36.4 6 8.86 14.5 7.58 4.70 4.16 30.8 2.88 1.28 62.0 38.0 7 8.86 13.9 7.63 4.30 4.56 27.0 3.33 1.23 56.4 43.6 8 8.95 10.3 8.03 5.35 3.60 25.6 2.68 0.92 66.6 33.4 9 8.89 10.0 8.00 5.45 3.44 25.8 2.55 0.89 68.1 31.9 10 9.60 13.1 8.34 4.85 4.75 26.5 3.49 1.26 58.2 41.8

From the results shown in Table 4, it was confirmed that the present invention effectively removes unreacted monomers and solvent from a polymer solution obtained after solution polymerization without shear of an extruder by using a gas-liquid separator and a stripper sequentially in the process of producing an EPDM elastic copolymer. Accordingly, the present invention can significantly improve the energy efficiency compared with the conventional method, and can produce a high molecular weight EPDM product suitably.

Claims (8)

A monomer composition comprising 40 to 70% by weight of ethylene, 15 to 55% 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 metallocene catalyst and a solvent, To produce a polymer solution comprising an ethylene-alpha olefin-diene based copolymer; And
Separating the solvent and the unreacted monomer from the polymer solution using a gas-liquid separator and a stripper in sequence, and recovering the ethylene-alpha olefin-diene copolymer,
Wherein the gas-liquid separator includes a step of removing the solvent and the unreacted monomer from the polymer solution at a temperature of the upper portion of the gas-liquid separator at a temperature of 150 to 160 DEG C and a pressure of 5 to 10 bar,
Wherein the stripper includes a step of adding water vapor as a carrier gas under a condition of a temperature of 140 to 180 ° C and a pressure of 4 to 10 bar to remove remaining solvent and unreacted monolayer from the polymer solution passed through the gas-
Wherein the metallocene catalyst comprises 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).
[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.
The method according to claim 1,
In the gas-liquid separator, 40 to 70% by weight of the total amount of the total materials excluding the entire polymer contained in the polymer solution is separated and removed,
Wherein the stripper comprises a step of separating and removing a residual solvent and unreacted monomers remaining in the remaining material excluding the polymer contained in the polymer solution.
The method for producing a ternary elastomeric copolymer according to claim 1, wherein in the stripper, recovering the solvent contained in the copolymer and the unreacted monomer to be within 10% by weight of the total copolymer content.
The method according to claim 1,
The content of the ethylene-alpha olefin-diene copolymer in the polymer solution before passing through the gas-liquid separator is 10 to 20% by weight, and the content of the ethylene-alpha olefin-diene copolymer contained in the polymer solution after passing through the gas- Is 20 to 50% by weight.
The method according to claim 1,
Wherein the solvent and the unreacted monomer separated in the gas-liquid separator and the stripper are reused in a copolymerization reaction for producing an ethylene-alpha olefin-diene copolymer.
The method of claim 1, further comprising, after the step of recovering the copolymer, producing the copolymer in the form of a bale or a pellet.
The process for producing a ternary elastomeric copolymer according to claim 1, wherein the catalyst composition further comprises at least one cocatalyst 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 .
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, 5-vinyl-2-norbornene, 1,4-hexadiene, and dicyclopentadiene.

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