KR20100126934A - Compound involving morpholine and transition metal complex thereof, and catalystic composition comprising transition metal complex - Google Patents

Abstract

PURPOSE: A morpholine group-introduced compound and transition metal compound using the same are provided to replace conventional metallocene catalyst. CONSTITUTION: A morphline group-introduced compound is denoted by chemical formula 1. A compound of chemical formula 2 is used as a catalyst for preparing an olefin polymer. The compound of chemical formula 2 is prepared using the compound of chemical formula 1. A catalyst composition contains the compound of chemical formula 2. The composition is additionally contains a compound of chemical formula 3(-[Al(R^5)-O]_a-), compound of chemical formula 4(J(R^5)_3) or compound of chemical formula 5([L-H]^+[ZA_4]^- or [L]^+[ZA_4]^-).

Description

Compound incorporating morpholine, transition metal compound using the same, and catalyst composition comprising the transition metal compound Thereof, And Catalystic Composition Comprising Transition Metal Complex

The present invention relates to a compound in which a morpholine group is introduced, a transition metal compound using the same, and a catalyst composition including the transition metal compound, and more particularly, to prepare a compound having a new structure in which a morpholine group is introduced. It relates to a transition metal compound prepared using the compound and a catalyst composition comprising the same.

Dow's CGC (constrained-geometry catalyst) catalyst, ie [(CH ₃ ) ₂ Si (η ^5- (CH ₃ ) ₄ C ₅ ) N ^t Bu] TiCl _2, is a homogeneous Ziegler-Natta olefin polymerization catalyst system ( Metallocene catalyst systems) are the most common and representative commercialized catalysts. The CGC catalyst activated by the cocatalyst has the following advantages over the existing metallocene catalysts. : (1) It produces a high molecular weight polymer with high activity even at high polymerization temperature. (2) The copolymerization of alpha-olefin with high steric hindrance such as 1-hexene and 1-octene is also very good. In addition, as various properties are known, efforts have been actively made in academia and industry to synthesize derivatives of CGC catalysts and use them as polymerization catalysts for various purposes.

One approach has been to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known to date are listed below [Figure 1] ( Chem . Rev. 2003 , 103 , 283).

 [Figure 1]

 Compounds listed in [Fig. 1] have ethyl (1), alkylphenyl (2), or phosphorus (3) bridges instead of CGC-structured silicon bridges, but are copolymerized with ethylene or alpha-olefins. It did not give excellent results in terms of activity or copolymerization performance compared to CGC.

[Figure 2]

Recently, as shown in [Figure 2], catalysts having different bridges in the CGC backbone, i.e., ligands incorporating phenyl groups, have been developed by the company and its partners ( Orgometallics , 2006 , 25 , 5122 and 2008 , 27). , 3907). These catalysts show similar levels of activity, molecular weight and 1-octene content as existing CGC catalysts in making ethylene / 1-octene copolymers at the current level.

The first technical problem to be achieved by the present invention is to provide a new multichelating compound incorporating a Morpholine group into one of the reported phenyl bridges.

The second technical problem to be achieved by the present invention is to provide a transition metal compound having a new structure and a catalyst composition containing the same using the compound.

The above and other objects of the present invention can be achieved by the present invention described below.

In order to achieve the above object, the present invention provides a compound of a novel structure represented by the following formula (1).

[Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, preferably methyl, ethyl, of 3 to 10 carbon atoms Normal alkyl, branched alkyl or cyclic alkyl.

In addition, the present invention provides a transition metal compound represented by the following Chemical Formula 2 using the compound.

[Formula 2]

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, preferably methyl, ethyl, of 3 to 10 carbon atoms Normal alkyl, branched alkyl or cyclic alkyl,

M is a Group 4 transition metal or Group 10 transition metal, and X is a halide, alkyl, or benzyl.

As described above, according to the present invention, there is an effect of providing a transition metal compound having a new structure that can be used as a catalyst for preparing an olefin polymer by replacing an existing metallocene catalyst.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The present invention focuses on developing a next-generation post metallocene catalyst by introducing a new structure deviating from the cyclopentadiene (Cp) ring, which is the basis of the existing CGC catalyst, in the structure of the catalyst for preparing the copolymer.

The inventors of the present invention have synthesized new compounds based on morpholine, and have confirmed that the metallocene compound prepared as a ligand compound also has activity as a catalyst for preparing an olefin polymer. Completed.

The present invention provides compounds represented by the following [Formula 1] by the synthesis method represented by the following Scheme 1 in order to achieve the first technical problem. However, the method for preparing the compound of Formula 1 is not limited to the following Scheme 1.

[Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, preferably methyl, ethyl, of 3 to 10 carbon atoms Normal alkyl, branched alkyl or cyclic alkyl, more preferably branched alkyl or cyclic alkyl having 3 to 8 carbon atoms such as methyl, ethyl or isopropyl, t-butyl and the like.

Scheme 1

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, preferably methyl, ethyl, of 3 to 10 carbon atoms Normal alkyl, branched alkyl or cyclic alkyl, more preferably branched alkyl or cyclic alkyl having 3 to 8 carbon atoms such as methyl, ethyl or isopropyl, t-butyl and the like.

The compounds of [Formula 1] are structures having phenoxy imine or Camphor group as a detailed functional group based on morpholine (Morpholine).

The morpholine group is a new type of ligand that has not been used until now. As shown in the above structure, the morpholine structure that forms a hexagonal ring with N and O at both ends has two coordination sites, N and O in itself, so that both sites can basically participate in coordination. In addition, the morpholine can change form freely (e.g., chair-like or boat-like, as in the case of normal cyclohexane), whereby N, O alone, or N and O together participate in coordination. Various number of coordination compounds can be provided, and the compound introduced therein has the advantage that the molecular weight distribution can be slightly increased due to the formation of at least two catalytically active sites in one catalyst.

The present invention, in order to achieve the second technical problem, the compound of [Formula 1] and various kinds of Group 4 transition metal precursor, for example TiCl ₄ , ZrBn ₄ , or TiCl ₂ (THF) _2, etc. To give the desired catalysts. In addition, various types of Group 10 transition metal precursors such as PdCl ₂ , NiCl ₂ (DME), NiPhCl (PPh ₃ ) ₂ , and the like are reacted to provide desired catalysts.

That is, the compounds represented by the following [Formula 2] may be synthesized by reacting the compounds represented by Formula 1 with the transition metal precursors, and these compounds may also be used as catalysts for preparing olefins.

[Formula 2]

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, preferably methyl, ethyl, of 3 to 10 carbon atoms Normal alkyl, branched alkyl or cyclic alkyl, more preferably branched alkyl or cyclic alkyl having 3 to 8 carbon atoms such as methyl, ethyl or isopropyl, t-butyl and the like.

M is a Group 4 transition metal or a Group 10 transition metal, preferably titanium (Ti) or zirconium (Zr),

X is halide, alkyl, or benzyl.

The compound of [Formula 2] according to the present invention can be used as a catalyst for preparing an olefin polymer.

The present invention also provides a catalyst composition comprising the metal compound of the formula (2). The catalyst composition according to the present invention may further include at least one cocatalyst compound selected from the group consisting of a compound of Formula 3, a compound of Formula 4, and a compound of Formula 5, in addition to the metal compound of Formula 2 .

(3)

^{- [Al (R 5) -O} ] a -

In which R ⁵ Are each independently 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, the hydrocarbyl is a monovalent group in the form of removing a hydrogen atom from a hydrocarbon.

[Formula 4]

J (R ⁵ ) ₃

Wherein J is aluminum or boron, each R ⁵ is independently 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, wherein the hydrocarbyl is hydro It is a monovalent group in the form which removed the hydrogen atom from carbon.

[Chemical Formula 5]

_{^{[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, and A is each independently at least one hydrogen atom is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy radicals And an aryl or alkyl radical having 6 to 20 carbon atoms, wherein the hydrocarbyl is a monovalent group in the form of removing a hydrogen atom from a hydrocarbon.

Among the promoter compounds, the compound of Formula 3 and the compound of Formula 4 may alternatively be represented by an alkylating agent, and the compound of Formula 5 may be represented by an activator.

The compound represented by Chemical Formula 3 is not particularly limited as long as it is an alkyl aluminoxane, but preferred examples thereof include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and particularly preferred compound is methyl aluminoxane.

The alkyl metal compound represented by Chemical Formula 4 is not particularly limited, but preferred examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, and tri-s. -Butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide , Dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and particularly preferred compounds are selected from trimethyl aluminum, triethyl aluminum, triisobutyl aluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetra (phenyl) boron, tributylammonium tetra (phenyl) boron, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethyl Ammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl ) Boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylamidiumdium tetra (phenyl) boron, N, N-diethylanilidedium tetra (phenyl) boron, N, N- Diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, trimethyl phosphonium tetra (phenyl) boron, triethyl ammonium Tetra (phenyl) aluminum, tributylammon Niumtetra (phenyl) aluminum, trimethylammoniumtetra (phenyl) aluminum, tripropylammoniumtetra (phenyl) aluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, tri Ethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetra (penta) Fluorophenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (phenyl) aluminum, N, N-diethylanilinium tetra (pentafluoro Phenyl) aluminum, diethyl ammonium tetra (pentafluorophenyl) aluminum, triphenyl phosphonium tetra (phenyl) aluminum, trimethyl phosphonium tetra (phenyl) aluminum, triethyl ammonium tetra (phenyl) aluminum, Tributylammonium tetra (phenyl) aluminum, trimethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, tripropylammonium tetra (p-tolyl) Boron, triethylammonium tetra (o, p-dimethylphenyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributyl ammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra (pentafluorophenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl ) Boron, N, N-diethylanilinium tetra (pentafluorophenyl) boron, diethyl ammonium tetra (pentafluorophenyl) boron, triphenyl phosphonium tetra (phenyl) boron, triphenyl carbonium tetra (p-trifluoromethylphenyl) boron, triphenylcarbonium tetra By phenyl) boron, trityl tetra (pentafluoro other fluorophenyl) boron, etc., but is not limited to this.

The catalyst composition is present in an activated state by a reaction between a transition metal compound and a promoter, and may be expressed in terms of an activated catalyst composition. However, since it is known in the art that the catalyst composition exists in an activated state, the term activated catalyst composition is not used separately herein. The catalyst composition can be used for olefin homopolymerization or copolymerization.

As a method for producing the catalyst composition according to the present invention, for example, the following method can be used.

Contacting the transition metal compound of Formula 2 with the compound of Formula 3 and / or the compound of Formula 4 in a first method to obtain a mixture; And adding a compound of Chemical Formula 5 to the mixture.

As a second method, a preparation method including contacting the transition metal compound of Formula 2 with the compound of Formula 3 may be used.

As a third method, a preparation method including contacting the transition metal compound of Formula 2 with the compound of Formula 5 may be used.

In the first method of preparing the catalyst composition, the molar ratio of the compound of Formula 3 and / or the compound of Formula 4 is preferably 1: 2 to 1: 5,000, More preferably, it is 1: 10-1: 1,000, Most preferably, it is 1: 20-1: 500. In addition, the molar ratio of the compound of Formula 5 to the transition metal compound of Formula 2 is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, most preferably 1: 2 to 1: 5.

When the amount of the compound of Formula 3 and / or the compound of Formula 4 is less than 2 moles with respect to 1 mole of the transition metal compound of Formula 2, the amount of alkylating agent is very small so that alkylation of the metal compound may not proceed completely. In case of exceeding 5,000 moles, alkylation of the metal compound is performed, but there is a problem in that activation of the alkylated metal compound is not completely performed due to a side reaction between the excess alkylating agent remaining and the activator of Formula 5.

In addition, when the amount of the compound of Formula 5 is less than 1 mole relative to 1 mole of the transition metal compound of Formula 2, the amount of the activator is relatively small, so that the activity of the catalyst composition generated due to the incomplete activation of the metal compound is not achieved. If there is a problem falling, if the excess exceeds 25 moles of the activation of the metal compound is completely made, there is a problem that the cost of the catalyst composition is economically low or the purity of the resulting polymer is inferior with the excess activator remaining.

In the second method of preparing the catalyst composition, the molar ratio of the compound of Formula 3 to the transition metal compound of Formula 2 is preferably from 1:10 to 1: 10,000, more preferably from 1: 100 to 1: 5,000, most preferably 1: 500 to 1: 2,000.

When the amount of the compound of Formula 3 is less than 10 moles with respect to 1 mole of the transition metal compound of Formula 2, the amount of the activator is relatively small, so that the activity of the catalyst composition that is not fully activated due to the inactivation of the metal compound is inferior. In the case of exceeding 10,000 moles, the metal compound is completely activated, but there is a problem in that the unit price of the catalyst composition is not economically economical due to the excess activator remaining or the purity of the produced polymer is inferior.

In the third method of preparing the catalyst composition, the molar ratio of the transition metal compound of Formula 2 to the compound of Formula 5 is preferably 1: 1 to 1:25, more preferably 1: 1 to 1 : 10, most preferably 1: 2 to 1: 5.

When the amount of the compound of Formula 5 is less than 1 mole relative to 1 mole of the transition metal compound of Formula 2, the amount of the activator is relatively small, so that the activity of the catalyst composition generated due to the incomplete activation of the metal compound is insufficient. When the amount of the compound of Formula 5 is more than 25 moles relative to 1 mole of the transition metal compound of Formula 2, the activation of the metal compound is completely performed, but the cost of the catalyst composition is economical with the remaining excess activator. As a result, there is a problem that the purity of the produced polymer is poor.

Hydrocarbon solvents such as pentane, hexane, heptane and the like or aromatic solvents such as benzene and toluene may be used as the reaction solvent in the preparation of the catalyst composition, but the solvent is not necessarily limited thereto. Can be.

In addition, the transition metal compounds and cocatalysts of Chemical Formula 2 may be used in a form supported on silica or alumina.

The present invention also provides a method for producing an olefin polymer using the catalyst composition. The process according to the invention can be carried out by contacting the catalyst composition with an olefin monomer. According to the method for producing the olefin polymer of the present invention, an olefin homopolymer or an olefin copolymer can be provided.

The most preferable polymerization process using the catalyst composition in the polymerization method of the present invention is a solution process, but is not limited thereto. When the catalyst composition is used together with an inorganic carrier such as silica, the catalyst composition can be applied to a slurry or gas phase process.

In the method for preparing a polymer according to the present invention, the catalyst composition is 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, toluene, benzene It can be injected by dissolving or diluting in an aromatic hydrocarbon solvent such as, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane, chlorobenzene and the like. The solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

Examples of the olefin monomer that can be polymerized using the metal compounds and the cocatalyst include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds may also be used. Polymerization is possible. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-aitocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethyl styrene, etc., These monomers may be mixed and copolymerized. When the olefin polymer is a copolymer of ethylene and other comonomers, the monomers constituting the copolymer are in the group consisting of propylene, 1-butene, 1-hexene, and 4-methyl-1-pentene, and 1-octene It is preferred that it is at least one comonomer selected.

In particular, in the process for producing the olefin polymer according to the present invention, the catalyst composition is not only at the reaction temperature conventionally used, but also at a high reaction temperature of 90 ° C. or higher, even at 140 ° C. or higher. Copolymerization of monomers with large steric hindrance is possible, and various substituents are introduced into tridentate ligands containing heteroatoms to easily control the electronic and steric environment around the metal, and ultimately the structure and physical properties of the resulting polyolefin Can be adjusted.

Hereinafter, the polymerization process of the olefin polymer is exemplified, but this is only for the purpose of illustrating the present invention, and the scope of the present invention is not limited by the following contents.

The reactor used in the process for producing the polymer according to the invention is preferably a continuous stirred reactor (CSTR) or a continuous flow reactor (PFR). Preferably, one or two or more reactors are arranged in series or in parallel. In addition, the preparation method preferably further comprises a separator for continuously separating the solvent and unreacted monomer from the reaction mixture.

When the method of preparing a polymer according to the present invention is performed in a continuous solution polymerization process, it may be composed of a catalytic process, a polymerization process, a solvent separation process, and a recovery process step.

a) catalytic process

The catalyst composition according to the present invention may be injected by dissolving or diluting an aliphatic or aromatic solvent having 5 to 12 carbon atoms or unsubstituted with a halogen suitable for an 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, benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane, chlorobenzene And the like can be used. The solvent used here is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating with a small amount of alkylaluminum or the like, and can also be carried out using an excessive amount of a promoter.

b) polymerization process

The polymerization process is carried out by introduction of at least one olefin monomer and a catalyst composition comprising the transition metal compound of Formula 2 and a promoter in the reactor. In the case of solution phase and slurry phase polymerization, a 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 monomer to 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 10: 1 to 1: 10000, preferably 5: 1 to 1: 100, most preferably 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, which causes a problem in transferring the produced polymer. When the molar ratio of the solvent exceeds 1: 10000, Since the amount is more than necessary, there are problems such as an increase in equipment and an increase in energy costs due to the purification of the solvent.

The solvent is preferably introduced into the reactor at a temperature of −40 ° C. to 150 ° C. using a heater or a freezer, whereby the polymerization is started together with the monomer and the catalyst composition. When the temperature of the solvent is less than -40 ℃, there will be some differences depending on the reaction amount, but the temperature of the solvent is too low, the reaction temperature is also accompanied by a problem of temperature control difficult, if the solvent exceeds 150 ℃ Too high a temperature of the reaction heat is difficult to react due to the reaction.

A high capacity pump raises the pressure above 50 bar to feed the feeds (solvent, monomer, catalyst composition, etc.), thereby passing the mixture of feeds without further pumping between the reactor arrangement, pressure drop device and separator. You can.

The internal temperature of the reactor suitable for the present invention, ie the polymerization reaction temperature, is -15 ° C to 300 ° C, preferably 50 ° C to 200 ° C, most preferably 100 ° C to 200 ° C. If the internal temperature is less than -15 ℃, there is a problem that the reaction rate is low, the productivity is lowered, and if it exceeds 300 ℃ may cause problems such as the generation of impurities due to side reactions and discoloration, such as carbonization of the polymer.

The internal pressure of the reactor suitable in the present invention is 1 bar to 300 bar, preferably 30 bar to 200 bar, most preferably 50 bar to 100 bar. When the internal pressure is less than 1 bar, the reaction rate is low, the productivity is low, and there is a problem due to evaporation of the solvent used, and when it exceeds 300 bar, there is a problem of an increase in equipment costs such as device cost according to high pressure.

The polymer produced in the reactor is maintained at a concentration of less than 20% by weight in the solvent and is preferably passed to the first solvent separation process for solvent removal after a short residence time. The residence time of the resulting polymer in the reactor is 1 minute to 10 hours, preferably 3 minutes to 1 hour, most preferably 5 minutes to 30 minutes. If the residence time is less than 1 minute, there are problems such as productivity loss and catalyst loss due to a short residence time, and increase in manufacturing cost, and in the case of more than 10 hours, depending on the reaction longer than the appropriate active period of the catalyst As a result, the reactor becomes large, and thus, there is a problem of increasing equipment cost.

c) solvent separation process

The solvent separation process is carried out 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 to about 200 ° C. to 230 ° C. through a heater, and then the pressure is lowered through a pressure drop device to vaporize unreacted raw materials and solvent in the first separator.

The pressure in the separator at this time is 1 bar to 30 bar, preferably 1 bar to 10 bar, most preferably 3 bar to 8 bar. The temperature in the separator is suitably 150 ° C to 250 ° C, preferably 170 ° C to 230 ° C, most preferably 180 ° C to 230 ° C.

If the pressure in the separator is less than 1 bar, the content of the polymer is increased, there is a problem in the transfer, if it exceeds 30 bar there is a problem that the separation of the solvent used in the polymerization process is difficult. In addition, when the temperature in the separator is less than 150 ° C., the viscosity of the copolymer and its mixture is increased, and there is a problem in transportation. When the temperature exceeds 250 ° C., there is a problem of discoloration due to carbonization of the polymer due to high temperature.

The solvent vaporized in the separator can be recycled to the condensed reactor in the overhead system. The first step of solvent separation yields a polymer solution concentrated up to 65%, which is transferred to the second separator by a transfer pump through a heater, where the separation of residual solvents takes place. In order to prevent the deformation of the polymer due to the high temperature while passing through the heater, a thermal stabilizer is added and a reaction inhibitor is injected into the heater together with the thermal stabilizer to suppress the reaction of the polymer due to the residual activity of the activator 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 the granulated polymer can be obtained by passing through the cooling water and the cutter. In the second separation process, the gasified solvent and other unreacted monomers can be sent to a recovery process for reuse after purification.

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 that acts 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 from a vacuum pump, and thus after purification in a recovery process. It is preferred to be reused.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples.

[Example]

The synthesis of all metal complexes and the preparation of experiments are carried out in a dry nitrogen atmosphere using dry box technology or using dry glass apparatus. All solvents used are HPLC grade and dried before use.

Example  One

Morpholino Phenoxyimine  Produce

250 mL of 1.2 g (5.12 mmol) of 3,5-di-tert-butyl-2-hydroxybenzaldehyde and 0.83 g (4.66 mmol) of morpholinoamine Place in Schlenk flask and dissolve in 30 mL of toluene. The yellow reaction solution was refluxed at 100 ° C. for 24 hours and then the solvent was removed using a depressurization apparatus to give the result as a white solid.

¹ H NMR (500 MHz, CDCl ₃ ): 1.32 (s, 9H, tibutyl), 1.47 (s, 9H, tibutyl), 3.01-3.04 (m, 4H, morpholine CH ₂ ), 3.86-3.90 (m , 4H, morpholine CH ₂ ), 7.02-7.10 (m, 2H, phenyl), 7.17-7.24 (m, 2H, phenyl). 7.24 (m, 1H, phenyl), 7.43-7.44 (m, 1H, phenyl), 8.69 (s, 1H, imine), 14.3 (s, 1H, phenoxyalcohol).

Example  2

Morpholino Phenoxyimine - TiCl ₃  of  Manufacture (catalyst 1)

100 mg (0.253 mmol) of the morpholino phenoxy imine prepared in Example 1 was dissolved in 10 mL toluene, and the temperature was lowered to -78 ° C. 0.11 mL (2.5M in hexane, 0.278 mmol) of n-BuLi was slowly injected into the reaction solution, and then stirred for 3 hours while slowly raising the temperature to room temperature. After lowering the temperature again, 0.126 mL (1M in toluene, 0.126 mmol) of TiCl ₄ is slowly added, and the temperature is slowly raised to room temperature.

After stirring the reaction solution at room temperature overnight, toluene was removed under reduced pressure and hexane was poured to form a solid. The solid was filtered and dried under reduced pressure to yield the result as a pale yellow solid (yield: 60%).

¹ H NMR (500 MHz, CDCl ₃ ): 1.34 (s, 18H, tibutyl), 1.49 (s, 18H, tibutyl), 3.04-3.09 (m, 8H, morpholine CH ₂ ), 3.88-3.95 (m , 8H, morpholine CH ₂ ), 7.02-7.46 (m, 12H, phenyl), 8.71 (s, 2H, imine).

Example  3 <ethylene polymerization>

100 mL of toluene is added to a 500 mL Andrews Glass reactor, and the reactor is preheated to 70 ° C. Using a syringe, 3 umol of the catalyst 1 prepared in Example 2 and 12 umol of trityl tetrakis (pentafluorophenyl) borate cocatalyst are sequentially filled. At this time, an ethylene pressure of 2 bar was applied and the polymerization reaction was carried out for 10 minutes, and then the remaining ethylene was removed, and the polymer solution was precipitated by adding excess methanol.

The obtained polymer is dried in a 60 ° C. vacuum oven for at least 24 hours. The polymerization conditions of Example 3 are shown in Table 1 below.

Example  4 <ethylene polymerization>

3 umol of the catalyst 1 prepared in Example 2 was used as in Example 3, and a polymer was prepared in the same manner as in Example 3, except that the reaction temperature was adjusted to 90 ° C. The polymerization conditions of Example 4 are shown in Table 1 below.

Example  5 <ethylene polymerization>

A polymer was prepared in the same manner as in Example 4, except that 5 umol of Catalyst 1 prepared in Example 2 was used. The polymerization conditions of Example 5 are shown in Table 1 below.

Comparative example  1 <ethylene polymerization>

100 mL of toluene is added to a 500 mL Andrews Glass reactor, and the reactor is preheated to 70 ° C. Using a syringe, 3 umol of the following CGC catalyst and 12 umol of trityl tetrakis (pentafluorophenyl) borate cocatalyst are filled in sequence. At this time, an ethylene pressure of 2 bar was added, the copolymerization reaction was carried out for 10 minutes, the remaining ethylene was removed, and the polymer solution was precipitated by adding excess methanol.

The obtained polymer is dried in a 60 ° C. vacuum oven for at least 24 hours. The polymerization conditions of Comparative Example 1 are shown in Table 1 below.

Comparative example  2 <ethylene polymerization>

A polymer was prepared in the same manner as in Comparative Example 1, except that the reaction temperature was adjusted to 90 ° C. in Comparative Example 1. The polymerization conditions of Comparative Example 2 are shown in Table 1 below.

catalyst Catalytic amount
(umol) Temperature
(℃) Ethylene
(bar) Promoter Promoter amount
(umol) Example 3 Catalyst 1 3 70 2 Borate
(Borate) 12 Example 4 Catalyst 1 3 90 2 Borate
(Borate) 12 Example 5 Catalyst 1 5 90 2 Borate
(Borate) 15 Comparative Example 1 CGC 3 70 2 Borate
(Borate) 12 Comparative Example 2 CGC 3 90 2 Borate
(Borate) 12

Test Example

The polymers prepared in Examples 3 to 5 and Comparative Examples 1 to 2 were evaluated in the following manners, and the results are shown in Table 2 below.

The organic reagents and solvents used in the examples and comparative examples were purchased from Aldrich and Merck and purified by standard methods.

Molecular weight distribution (PDI): The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using gel permeation chromatography (GPC), and the weight average molecular weight was divided and divided into the number average molecular weights.

* Melting point (Tm) of polymer: Measured using DSC (Differential Scanning Calorimeter) 2920 manufactured by TA. That is, the temperature was increased to 200 ° C., then maintained at that temperature for 5 minutes, then lowered to 30 ° C., and the temperature increased again to make the top of the DSC curve the melting point. At this time, the rate of temperature rise and fall is 10 ° C./min, and a melting point is obtained while the second temperature is rising.

Density of polymer: A sample treated with an antioxidant (1,000 ppm) was made into a sheet having a thickness of 3 mm and a radius of 2 cm using a 180 ° C. press mold, and cooled to 10 ° C./min, Mettler. Measured on the balance.

Yield
(g) Mw PDI Tm
(℃) density
(g / cm ³⁾ Example 3 9.17 120,620 2.4 130.4 0.942 Example 4 9.05 124,100 2.5 130.1 0.939 Example 5 11.48 117,850 2.5 129.8 0.939 Comparative Example 1 8.22 101,500 2.1 127.5 0.936 Comparative Example 2 7.95 110,210 2.3 128.2 0.934

As shown in Table 2, it can be seen that the catalyst composition comprising the transition metal compound according to the present invention exhibits catalytic activity when polymerizing the olefin polymer (Examples 3 to 5).

Although the present invention has been described in detail with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the present invention, and such modifications and modifications fall within the scope of the appended claims. It is also natural.

Claims (15)

The compound represented by following [Formula 1]. [Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl. The method of claim 1, R ₁ and R ₂ are each independently methyl, ethyl, normal alkyl having 3 to 10 carbon atoms, branched alkyl or cyclic alkyl. The manufacturing method of compound 1a by reaction represented by following Reaction [scheme 1]. Scheme 1

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl. The method of claim 3, wherein R ₁ and R ₂ are each independently methyl, ethyl, normal alkyl, branched alkyl or cyclic alkyl having 3 to 10 carbon atoms. The compound represented by following [Formula 2]. [Formula 2]

Wherein R ₁ , R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, M is a Group 4 transition metal or Group 10 transition metal, and X is a halide, alkyl, or benzyl. The method of claim 5, R ₁ and R ₂ are each independently methyl, ethyl, normal alkyl having 3 to 10 carbon atoms, branched alkyl or cyclic alkyl, characterized in that The method of claim 5, The compound is used as a catalyst for producing an olefin polymer. The method of claim 5, The compound of Formula 2 is characterized in that it is prepared using a compound of formula (1). [Formula 1]

Wherein R ₁ and R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl. Catalyst composition comprising a compound represented by the following [Formula 2]. [Formula 2]

Wherein R ₁ , R ₂ are each independently hydrogen, normal alkyl of 1 to 20 carbon atoms, branched alkyl or cyclic alkyl, aryl, alkenyl or alkylaryl, M is a Group 4 transition metal or Group 10 transition metal, and X is a halide, alkyl, or benzyl. The method of claim 9, The composition of claim 1, wherein the composition is used for the production of olefin polymers. The method of claim 9, The composition is a catalyst composition, characterized in that it further comprises at least one compound selected from the group consisting of a compound of formula (3), a compound of formula (4) and a compound of formula (5). (3) ^{- [Al (R 5) -O} ] a - In which R ⁵ Are each independently 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, the hydrocarbyl is a monovalent group in the form of removing a hydrogen atom from a hydrocarbon. [Formula 4] J (R ⁵ ) ₃ Wherein J is aluminum or boron, each R ⁵ is independently 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, wherein the hydrocarbyl is hydro It is a monovalent group in the form which removed the hydrogen atom from carbon. [Chemical Formula 5] _{^{[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, and A is each independently at least one hydrogen atom is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy or phenoxy radicals And an aryl or alkyl radical having 6 to 20 carbon atoms, wherein the hydrocarbyl is a monovalent group in the form of removing a hydrogen atom from a hydrocarbon. The method of claim 11, When the catalyst composition comprises a compound of formula 3, a compound of formula 4 and a compound of formula 5, The molar ratio of the compound of Formula 3 or the compound of Formula 4 is 1: 2 to 1: 5,000 with respect to the compound of Formula 2, Catalyst composition, characterized in that the molar ratio of the compound of Formula 5 to the compound of Formula 2 is 1: 1 to 1:25. The method of claim 11, When the catalyst composition includes the compound of Formula 3, the molar ratio of the compound of Formula 3 to the compound of Formula 2 is 1:10 to 1: 10,000. The method of claim 11, When the catalyst composition includes the compound of Formula 5, the molar ratio of the compound of Formula 5 to the compound of Formula 2 is 1: 1 to 1:25, characterized in that. A method for producing an olefin polymer comprising the step of preparing an olefin polymer from an olefin monomer using the catalyst composition of claim 9.