KR20150048462A - The catalysts consist of aniline derivatives and cyclopentadiene derivatives, and their applications to olefine polymerization - Google Patents
The catalysts consist of aniline derivatives and cyclopentadiene derivatives, and their applications to olefine polymerization Download PDFInfo
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Abstract
Description
The present invention relates to a ligand in which an aniline derivative and a cyclopentadiene derivative are combined, an organometallic compound containing the ligand compound, a catalyst composition comprising the organometallic compound, a process for preparing the same, and a process for preparing an olefin polymer using the catalyst composition ≪ / RTI >
In the early 1990s, DOW announced the use of [Me 2 Si (Me 4 C 5 ) N t Bu] TiCl 2 (Constrained-Geometry Catalyst, CGC) (US Pat. No. 5,064,802) (1) produce high molecular weight polymers with high activity even at high polymerization temperatures, (2) react with 1-hexene and It is also excellent in the copolymerization of α-olefins with large steric hindrance such as 1-octene. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.
One approach is to synthesize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges and olefin polymerization using the same. Opening exemplary metal compounds known to date are: (Chem. Rev. 2003, 103 , 283).
The compounds listed above have been introduced with phosphorus (1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges, respectively, instead of the CGC structure of silicon bridges, In the case of the copolymerization, there were no excellent results in terms of activity or copolymerization performance in comparison with CGC.
In addition, as another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted. The examples are summarized as follows.
The compound (5) is reported by TJ Marks et al., And is characterized in that the Cp derivative and the oxydolidine are cross-linked by ortho-phenylene groups ( Organometallics 1997 , 16 , 5958). Compounds having the same cross-linking and polymerization using them have also been reported by Mu et al. ( Organometallics 2004 , 23 , 540). Also, Rothwell et al . ( Chem . Commun . 2003 , 1034) have reported that an indenyl ligand and an oxydol ligand are bridged by the same ortho-phenylene group. The compound (6) is reported by Whitby et al., And is characterized in that a cyclopentadienyl ligand and an oxydol ligand are bridged by three carbon atoms ( Organometallics 1999 , 18 , 348). These catalysts are synthesized from syndiotactic syndiotactic polystyrene polymerization. Similar compounds have also been reported by Hessen et al. ( Organometallics 1998 , 17 , 1652). (7) above is a compound represented by the feature that seems to be reported include Rau, high temperature and high pressure (210 ℃, 150 MPa) of ethylene and ethylene / 1-hexene copolymer in the active (J. Organomet.Chem. 2000, 608 , 71). Also, the synthesis of the catalyst (8) having similar structure and the high-temperature high-pressure polymerization using the same were patented by Sumitomo Co. (US Pat. No. 6,548,686).
Recently, compounds such as the above compound (9) having a pyridyl-amide ligand deviating from the CGC structure have been reported by DOW (US 2004/0220050, J. Am . Chem . Soc . 2007 , 129 , 7831). These catalysts are capable of high temperature polymerization and have multiple active sites and thus exhibit activity against ethylene / octene copolymerization with a broad molecular weight distribution.
On the other hand, Mitsui Japan has developed a transition metal compound (Ti, Zr) having a basic skeleton of phenoxyimine, showing excellent activity and ability such as controlling various polypropylene as well as living polymerization, as well as polyethylene. This catalyst is characterized by the fact that cyclopentadiene ligands, which are important skeletons of conventional metallocene catalysts and CGCs, are not present in the catalyst structure. As a result, this catalyst began to receive its spotlight as a post-metallocene, ie, a next-generation catalyst outside the metallocene structure. This catalyst was named FI catalyst 10, and the activity and efficiency of the catalyst were investigated in detail as the various substituents were changed around the basic structure of the catalyst, and it has been quoted in numerous literatures at present ( J. Am . Chem. Soc . 2001, 123, 6847 and 2002 , 124, 3327).
Recently, LG Chem developed a catalyst (11, 12) having another bridge, that is, a ligand in which a phenyl group is introduced, in the CGC backbone ( Organometallics , 2006 , 25 , 5122 and 2008 , 27 , 3907). These catalysts have the same activity level, molecular weight, and 1-octene content as those of conventional CGC in the production of ethylene / 1-octene copolymer.
An object of the present invention is to develop a catalyst having a structure in which a Cp derivative and an aniline derivative are combined with each other to bond a nitrogen atom of Cp and aniline to a central metal.
Accordingly, it is an object of the present invention to provide various types of ligand compounds having a structure in which a Cp derivative and an aniline derivative are connected to each other as a basic skeleton.
Another object of the present invention is to provide an organometallic compound wherein the transition metal of group 4 to group 12 is a central metal using the ligand.
It is still another object of the present invention to provide a catalyst composition comprising the organometallic compound.
It is still another object of the present invention to provide a method for producing a catalyst composition comprising the metal compound.
It is a further object of the present invention to provide a process for preparing an olefin polymer using the catalyst composition.
According to an aspect of the present invention, there is provided an organometallic compound represented by Chemical Formula (1).
In Formula 1,
R 1 , R 2 , R 3 , R 4 and R 5, which may be the same or different from each other, are each independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 60 carbon atoms, Aryl or arylene of from 60 to 60 carbon atoms, cyclodienyl of from 5 to 60 carbon atoms, alkenyl or alkenylene of from 2 to 20 carbon atoms, alkylaryl of from 7 to 60 carbon atoms and arylalkyl of from 7 to 60 carbon atoms;
M is a Group 3 to Group 12 metal or lanthanide series metal, preferably titanium (Ti), zirconium (Zr), hafnium (Hf), but is not limited thereto;
X 1 and X 2 may be the same or different and each independently represents a halogen radical, an alkylamido of 1 to 20 carbon atoms, a silylalkyl of 1 to 20 carbon atoms, an arylamido of 6 to 60 carbon atoms, an arylamido of 1 to 20 carbon atoms Alkyl, an alkenyl or alkenylene having 2 to 20 carbon atoms, an aryl or arylene having 6 to 60 carbon atoms, an alkylaryl having 7 to 60 carbon atoms, an arylalkyl having 7 to 60 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms ≪ / RTI >
m and n are each an integer of 0 to 4;
In order to achieve the above object, a second aspect of the present invention provides a catalyst composition comprising the organometallic compound.
A third aspect of the present invention provides a process for preparing the catalyst composition.
A fourth aspect of the present invention provides a process for preparing an olefin polymer using the catalyst composition.
According to the present invention, there is no known or synthesized organometallic compound having the new ligand. The introduction of various substituents into Cp or aniline can easily control the electronic and stereoscopic environment around the metal, and ultimately, It is possible to control the structure and physical properties of the polyolefin.
Hereinafter, the present invention will be described in detail.
The present invention provides an organometallic compound represented by the above formula (1).
Each substituent in Formula 1 will be described in detail as follows.
The alkyl has 1 to 20 carbons, and is linear or branched.
The alkenyl or alkenylene has from 2 to 20 carbons and is linear or branched.
The aryl or arylene has 6 to 60 carbons and may be a single ring or a condensed ring of two or more rings. Preferable examples of aryl include, but are not limited to, phenyl, naphthyl, fluorenyl, and the like.
The cyclodienyl has 5 to 60 carbons, including, but not limited to, cyclopentadienyl and the like.
The cycloalkyl has 5 to 60 carbons, and includes, but is not limited to, pentane, hexane, heptane and the like.
Specific examples of the organometallic compound of Formula 1 may be a compound represented by one of the following structural formulas, but the present invention is not limited thereto.
The synthesis method of the organometallic compound of formula (1) is as follows. Methyl-2-bromoaniline is prepared by introducing a methyl group into a nitrogen atom using 2-bromoaniline as a starting material, trimethylsilane is introduced into a nitrogen atom as a protecting group, bromine is substituted with lithium, and this is reacted with dichlorodimethylsilane To give N-methyl-2-chlorodimethylsilyl aniline. This compound is mixed with a solution of Cp derivative reacted with butyl lithium prepared separately and reacted with water, followed by treatment to synthesize the final ligand. The synthesized ligand may be reacted with butyllithium and then reacted with a metal source to prepare the compound of Formula 1.
The present invention also provides a catalyst composition comprising the organometallic compound of formula (1).
The catalyst composition according to the present invention may further comprise at least one cocatalyst compound selected from the group consisting of a compound represented by the following formula 2, a compound represented by the following formula 3 and a compound represented by the following formula 4, in addition to the organometallic compound represented by the above formula .
(2)
- [Al (R 6) -O ] a -
R 6 may be the same or different from each other and is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and a is an integer of 2 or more. Here, "hydrocarbyl" is a monovalent form in which a hydrogen atom is removed from a hydrocarbon.
(3)
J (R < 6 >) 3
Wherein J is aluminum or boron, and R < 6 > is as defined in formula (2).
[Chemical Formula 4]
[LH] + [ZA 4 ] - or [L] + [ZA 4 ] -
Wherein 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 at least one hydrogen atom may be substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms , An aryl or an alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical.
Among the above-described co-catalyst compounds, the compound of Formula 2 and the compound of Formula 3 may alternatively be represented by an alkylating agent, and the compound of Formula 4 may be represented by an activating agent.
The compound of Formula 2 is not particularly limited as long as it is alkylaluminoxane, and preferable examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. Particularly preferred compound is methylaluminoxane.
The alkyl metal compound of Formula 3 is not particularly limited but preferable examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro 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 Trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like. Particularly preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
Examples of the compound of Formula 4 include triethylammoniumtetra (phenyl) boron, tributylammoniumtetra (phenyl) boron, trimethylammoniumtetra (phenyl) boron, tripropylammoniumtetra (phenyl) boron, trimethylammonium (P-tolyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron , N, N-diethylamidinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethyl (Pentafluorophenyl) boron, diethylammoniumtetra (pentafluorophenyl) boron, triphenylphosphonium tetra (phenyl) boron, trimethylphosphonium tetra (phenyl) boron, triethylammonium tetra Phenyl) aluminum, tributylammonium tetra (Phenyl) aluminum, trimethylammoniumtetra (phenyl) aluminum, tripropylammoniumtetra (phenyl) aluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (Phenyl) aluminum, N, N-diethylaniliniumtetra (phenyl) aluminum, N, N-diethylaniliniumtetra (Phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammoniumtetra (phenyl) aluminum, tributyl (triphenylphosphine) (P-tolyl) boron, tripropylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra (phenyl) boron, (O, p-dimethylphenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (p N, N-diethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron (trifluoromethylphenyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, (Pentafluorophenyl) boron, triphenylphosphonium tetra (phenyl) boron, triphenylcobonium tetra (p (trifluoromethyl) -Trifluoromethylphenyl) boron, triphenylcarboniumtetra (pentafluoro < RTI ID = 0.0 > Phenyl), but is such as boron, trityl tetra (pentafluorophenyl) boron is not limited thereto.
The catalyst composition is in an activated state due to a reaction between the metal compound and the cocatalyst, and may be referred to as an activated catalyst composition. However, since it is well known in the art that the catalyst composition is present in an activated state, the term activated catalyst composition will not be used separately herein. The catalyst composition can be used for olefin mono-polymerization or copolymerization.
As a method for producing the catalyst composition according to the present invention, for example, the following method can be used.
First, contacting the organometallic compound of Formula 1 with the compound of Formula 2 and / or the compound of Formula 3 to obtain a mixture; And adding the compound of Formula 4 to the mixture.
Secondly, a method of preparing a catalyst composition by contacting the organometallic compound of Formula 1 with the compound of Formula 2 may be used.
Third, a method of preparing a catalyst composition by contacting the organometallic compound of Formula 1 with the compound of Formula 4 may be used.
In the first method of the present invention, the molar ratio of the compound of formula (2) to the compound of formula (3) relative to the organometallic compound of formula (1) is preferably 1: 2 to 1: 5,000, 1:10 to 1: 1,000, and most preferably 1:20 to 1: 500. The molar ratio of the organometallic compound of Formula 1 to the compound of Formula 4 is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, and most preferably 1: 1: 5.
When the amount of the compound of the formula (2) and the compound of the formula (3) is less than 2 mol per 1 mol of the organometallic compound of the formula (1), the amount of the alkylating agent is so small that the alkylation of the metal compound can not proceed completely. When the amount of the compound of Formula 2 and the compound of Formula 3 is more than 5,000 moles per mole of the organometallic compound of Formula 1, the alkylation of the metal compound is carried out, There is a problem in that activation of the alkylated metal compound can not be completely achieved due to side reactions between the activating agents of the general formula When the amount of the compound of the formula (4) is less than 1 mole per 1 mole of the organometallic compound of the formula (1), the amount of the activator is relatively small and the activation of the metal compound is not completely achieved. When the amount of the compound of the formula (4) is more than 25 mol per 1 mol of the organometallic compound of the formula (1), the activation of the metal compound is completely carried out. However, There is a problem that the purity of the polymer which is not economically produced or is produced is lowered.
In the second method, the molar ratio of the organometallic compound of Formula 1 to the compound of Formula 2 is preferably 1:10 to 1: 10,000, more preferably 1: 100 to 1: : 5,000, and most preferably from 1: 500 to 1: 2,000. When the amount of the compound of formula (2) is less than 10 moles per mole of the organometallic compound of formula (1), the amount of the activator is relatively small and the activation of the metal compound is not completely achieved, If the amount of the compound of Formula 2 is more than 10,000 moles per 1 mole of the organometallic compound of Formula 1, the activation of the metal compound is completely performed. However, Or the purity of the resulting polymer is lowered.
In the third method of the catalyst composition production method, the molar ratio of the organometallic compound of Formula 1 to the compound of Formula 4 is preferably 1: 1 to 1:25, more preferably 1: 1 to 1: : 10, and most preferably from 1: 2 to 1: 5.
In the preparation of the catalyst composition, hydrocarbon solvents such as pentane, hexane, heptane and the like, aromatic solvents such as benzene and toluene may be used as the reaction solvent, but not always limited thereto, and all solvents usable in the related art are used .
The organometallic compounds and cocatalysts of Formula 1 may also be supported on silica or alumina.
The present invention also provides a process for preparing an olefin polymer using the catalyst composition. The process for producing an olefin polymer of the present invention can be carried out by contacting the above-mentioned catalyst composition with an olefin-based monomer. According to the process for producing an olefin polymer of the present invention, an olefin homopolymer or an olefin copolymer can be provided.
In the polymerization method of the present invention, the most preferable polymerization process using the above catalyst composition is a solution process. When the catalyst composition is used together with an inorganic carrier such as silica, it is applicable to a slurry or a gas phase process.
In the process for producing a polymer according to the present invention, the catalyst composition may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane and isomers thereof, , A hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, chlorobenzene, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.
Examples of the olefin-based monomer polymerizable with the organometallic compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like. The diene olefin-based monomer or triene olefin-based monomer having two or more double bonds Can also be polymerized. Specific examples of the monomer include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, Butene, dicyclopentadiene, 1,4-butadiene, 1,4-butadiene, 1,3-butadiene, 1,3-butadiene, Pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene and the like. These two or more monomers may be mixed and copolymerized. When the olefin polymer is a copolymer of ethylene and another comonomer, the monomer constituting the copolymer is selected from the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl- It is preferably one or more comonomers selected.
Particularly, in the process for preparing an olefin polymer according to the present invention, the catalyst composition is used not only at the reaction temperature conventionally used but also at a reaction temperature of not lower than 90 ° C, even at a reaction temperature of not lower than 140 ° C, Copolymerization of monomers with high functionality is also possible. By introducing various substituents, it is possible to easily control the electronic and stereoscopic environment around the metal, and ultimately it is possible to control the structure and physical properties of the produced polyolefin.
Hereinafter, the polymerization process of the olefin polymer will be illustrated, but this is merely for the purpose of illustrating the present invention, and the scope of the present invention is not intended to be limited by the following description.
The reactor used in the process for preparing the polymer according to the present invention is preferably a continuously stirred reactor (CSTR) or a continuous flow reactor (PFR). It is preferable that two or more of the reactors are arranged in series or in parallel. It is also preferred that the process further comprises a separator for continuously separating the solvent and unreacted monomers from the reaction mixture.
When the process for producing a polymer according to the present invention is carried out by a continuous solution polymerization process, it can be composed of a catalytic process, a polymerization process, a solvent separation process, and a recovery process step, and more specifically, the following.
a) catalytic process
The catalyst composition according to the present invention can be injected by dissolving or diluting in an aliphatic or aromatic solvent having 5 to 12 carbon atoms which is unsubstituted or substituted with halogen suitable for the olefin polymerization process. For example, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof, aromatic hydrocarbon solvents such as toluene, xylene and benzene, hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene Can be used. The solvent used herein is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum or the like, and it is also possible to use a large amount of a cocatalyst.
b) Polymerization process
The polymerization process proceeds on the reactor by introducing the catalyst composition comprising the organometallic compound of formula (I) and the cocatalyst and one or more olefin monomers. In the case of solution phase and slurry polymerization, the solvent is injected onto the reactor. In the case of solution polymerization, a mixture of a solvent, a catalyst composition and a monomer is present in the reactor.
The molar ratio of the monomer to the solvent suitable for the reaction should be a ratio suitable for dissolving the raw material before the reaction and the polymer produced after the reaction. Specifically, the molar ratio of monomer to solvent is from 10: 1 to 1: 10000, preferably from 5: 1 to 1: 100, and most preferably from 1: 1 to 1:20. When the molar ratio of the solvent is less than 10: 1, the amount of the solvent is too small to increase the viscosity of the fluid, and there is a problem in transferring the resultant polymer. When the molar ratio of the solvent is more than 1: 10000, There is a problem such as an increase in equipment and an increase in energy cost due to the refining and recycling of the solvent.
Preferably, the solvent is introduced into the reactor at a temperature of -40 DEG C to 150 DEG C by using a heater or a freezer, whereby the polymerization reaction starts with the monomer and the catalyst composition. When the temperature of the solvent is less than -40 ° C, there is a slight difference depending on the amount of the reaction. However, since the temperature of the solvent is generally too low, the reaction temperature is also lowered and the temperature is difficult to control. The temperature of the solvent is too high, so that it is difficult to remove the heat of reaction due to the reaction.
A high capacity pump passes the mixture of feeds without further pumping between the reactor arrangement, the pressure drop device and the separator by feeding the feeds (solvent, monomer, catalyst composition, etc.) by raising the pressure to more than 50 bar .
The internal temperature of the reactor suitable for the present invention, i.e., the polymerization reaction temperature is -15 캜 to 300 캜, preferably 50 캜 to 200 캜, and most preferably 100 캜 to 200 캜. When the internal temperature is lower than -15 ° C, the reaction rate is low and productivity is lowered. When the internal temperature is higher than 300 ° C, problems such as generation of impurities due to side reactions and carbonization of the polymer may occur.
Suitable pressures in the reactor according to the invention are from 1 bar to 300 bar, preferably from 30 to 200 bar, most preferably from 50 to 100 bar. When the internal pressure is less than 1 bar, the reaction rate is low and the productivity is low, and there is a problem due to vaporization of the used solvent. When the internal pressure is more than 300 bar, there is a problem of equipment cost such as equipment cost due to high pressure.
The polymer produced in the reactor is preferably maintained at a concentration of less than 20 wt% in the solvent and is preferably transferred to the first solvent separation process for solvent removal after a short residence time. The residence time in the reactor of the resulting polymer is from 1 minute to 10 hours, preferably from 3 minutes to 1 hour, most preferably from 5 minutes to 30 minutes. When the residence time is less than 3 minutes, there is a problem such as a decrease in productivity and a loss of catalyst due to a short residence time, and an increase in manufacturing cost due to a short residence time. When the residence time exceeds 1 hour, There is a problem that the reactor cost is increased due to the increase of the reactor.
c) solvent separation process
A solvent separation process is performed by varying the solution temperature and pressure to remove the solvent present with the polymer exiting the reactor. For example, the polymer solution transferred from the reactor is heated through a heater from about 200 ° C to 230 ° C, and then the pressure is lowered through the pressure drop device, and the unreacted raw material and the solvent are vaporized in the first separator.
In this case, the pressure in the separator is suitably from 1 to 30 bar, preferably from 1 to 10 bar, and most preferably from 3 to 8 bar. The temperature in the separator is suitably 150 deg. C to 250 deg. C, preferably 170 deg. C to 230 deg. C, and most preferably 180 deg. C to 230 deg.
When the pressure in the separator is less than 1 bar, the content of the polymer increases and there is a problem in transferring. When the pressure is more than 30 bar, it is difficult to separate the solvent used in the polymerization process. When the temperature in the separator is lower than 150 ° C, the viscosity of the copolymer and its mixture increases, and there is a problem in transportation. When the temperature is less than 250 ° C, there is a problem of discoloration due to carbonization of the polymer due to denaturation at high temperature.
The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. When the first stage solvent separation process is performed, a concentrated polymer solution of up to 65% can be obtained, which is transferred to the second separator by the transfer pump through the heater, and the separation process for the residual solvent is performed in the second separator. In order to prevent deformation of polymer due to high temperature while passing through a heater, a heat stabilizer is added and a reaction inhibitor is injected with a heat stabilizer together with a heat stabilizer to suppress the reaction of the polymer due to the residual activity of the active substance present in the polymer solution do. The residual solvent in the polymer solution injected into the second separator is finally completely removed by a vacuum pump, and a granulated polymer can be obtained after passing through the cooling water and the cutter. In the second separation process, the gaseous solvent and other unreacted monomers can be sent to the recovery process for purification and reuse.
d) Recovery process
The organic solvent added with the raw material to the polymerization process may be recycled to the polymerization process together with the unreacted raw material in the primary solvent separation process. However, the solvent recovered in the secondary solvent separation process contains a large amount of water acting as a catalyst poison in the solvent due to contamination due to incorporation of a reaction inhibitor to stop the catalytic activity and steam supply in the vacuum pump, It is preferable to be reused.
Claims (13)
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 , R 3 , R 4 and R 5, which may be the same or different from each other, are each independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 60 carbon atoms, Aryl or arylene of from 60 to 60 carbon atoms, cyclodienyl of from 5 to 60 carbon atoms, alkenyl or alkenylene of from 2 to 20 carbon atoms, alkylaryl of from 7 to 60 carbon atoms and arylalkyl of from 7 to 60 carbon atoms;
M is a Group 3 to Group 12 metal or lanthanide series metal, preferably titanium (Ti), zirconium (Zr), hafnium (Hf), but is not limited thereto;
X 1 and X 2 may be the same or different and each independently represents a halogen radical, an alkylamido of 1 to 20 carbon atoms, a silylalkyl of 1 to 20 carbon atoms, an arylamido of 6 to 60 carbon atoms, an arylamido of 1 to 20 carbon atoms Alkyl, an alkenyl or alkenylene having 2 to 20 carbon atoms, an aryl or arylene having 6 to 60 carbon atoms, an alkylaryl having 7 to 60 carbon atoms, an arylalkyl having 7 to 60 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms ≪ / RTI >
m and n are each an integer of 0 to 4;
1. A catalyst composition comprising at least one promoter compound selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3) and a compound represented by the following formula (4)
(2)
- [Al (R 6) -O ] a -
In the above formula, R 6 may be the same or different from each other and is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more;
(3)
J (R < 6 >) 3
Wherein J is aluminum or boron, R < 6 > is as defined in Formula 2 above;
[Chemical Formula 4]
[LH] + [ZA 4 ] - or [L] + [ZA 4 ] -
Wherein 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 at least one hydrogen atom may be substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms , An aryl or an alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical.
[Chemical Formula 1]
In Formula 1,
ROne, R2, R3 , R4, And R5 May be the same or different and are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 60 carbon atoms, an aryl or arylene group having 6 to 60 carbon atoms, Alkenyl or alkenylene having 2 to 20 carbon atoms, alkylaryl having 7 to 60 carbon atoms, and arylalkyl having 7 to 60 carbon atoms;
M is a metal of group 3 to 12 or a lanthanide series metal;
XOne And X2Are each independently selected from the group consisting of halogen radicals, alkylamido of 1 to 20 carbon atoms, silylalkyl of 1 to 20 carbon atoms, arylamido of 6 to 60 carbon atoms, alkyl of 1 to 20 carbon atoms, An aryl group having 6 to 60 carbon atoms, an alkylaryl group having 7 to 60 carbon atoms, an arylalkyl group having 7 to 60 carbon atoms, and an alkylidene radical having 1 to 20 carbon atoms;
m and n are each an integer of 0 to 4;
(2)
- [Al (R6) -O]a-
Wherein R6May be the same or different and are a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more;
(3)
J (R6)3
Wherein J is aluminum or boron, R6Is as defined in Formula 2;
[Chemical Formula 4]
[L-H] <+[ZA4]- Or [L]+[ZA4]-
Wherein 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 at least one hydrogen atom may be substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms , An aryl or an alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical.
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 , R 3 , R 4 and R 5, which may be the same or different from each other, are each independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 60 carbon atoms, An aryl of from 60 to 60 carbon atoms, a cyclodienylene group having from 5 to 60 carbon atoms, an alkenyl having from 2 to 20 carbon atoms, an alkylaryl having from 7 to 60 carbon atoms, and an arylalkyl having from 7 to 60 carbon atoms;
M is a metal of group 3 to 12 or a lanthanide series metal;
X 1 and X 2 may be the same or different and each independently represents a halogen radical, an alkylamido of 1 to 20 carbon atoms, a silylalkyl of 1 to 20 carbon atoms, an arylamido of 6 to 60 carbon atoms, an arylamido of 1 to 20 carbon atoms Alkyl, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 60 carbon atoms, alkylaryl having 7 to 60 carbon atoms, arylalkyl having 7 to 60 carbon atoms, and alkylidene radical having 1 to 20 carbon atoms;
m and n are each an integer of 0 to 4;
(2)
- [Al (R 6) -O ] a -
R 6 may be the same or different from each other and is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, and a is an integer of 2 or more.
[Chemical Formula 1]
In Formula 1,
R 1 , R 2 , R 3 , R 4 and R 5, which may be the same or different from each other, are each independently selected from the group consisting of alkyl of 1 to 20 carbon atoms, cycloalkyl of 5 to 60 carbon atoms, An aryl of from 60 to 60 carbon atoms, a cyclodienylene group having from 5 to 60 carbon atoms, an alkenyl having from 2 to 20 carbon atoms, an alkylaryl having from 7 to 60 carbon atoms, and an arylalkyl having from 7 to 60 carbon atoms;
M is a metal of group 3 to 12 or a lanthanide series metal;
X 1 and X 2 may be the same or different and each independently represents a halogen radical, an alkylamido of 1 to 20 carbon atoms, a silylalkyl of 1 to 20 carbon atoms, an arylamido of 6 to 60 carbon atoms, an arylamido of 1 to 20 carbon atoms Alkyl, alkenyl having 2 to 20 carbon atoms, aryl having 6 to 60 carbon atoms, alkylaryl having 7 to 60 carbon atoms, arylalkyl having 7 to 60 carbon atoms, and alkylidene radical having 1 to 20 carbon atoms;
m and n are each an integer of 0 to 4;
[Chemical Formula 4]
[LH] + [ZA 4 ] - or [L] + [ZA 4 ] -
Wherein 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 at least one hydrogen atom may be substituted with halogen, hydrocarbyl having 1 to 20 carbon atoms , An aryl or an alkyl radical having 6 to 20 carbon atoms substituted with an alkoxy or phenoxy radical.
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