KR101670486B1 - Transition metal compound, catalyst composition for preparing poly-olefin, preparation method of poly-olefin - Google Patents

Abstract

The present invention relates to a method for producing a polyolefin comprising a transition metal compound having a specific chemical structure, a catalyst composition for synthesizing polyolefin comprising the transition metal compound, and a step of polymerizing ethylene in the presence of the catalyst for synthesizing polyolefin will be.

Description

TECHNICAL FIELD [0001] The present invention relates to a transition metal compound, a catalyst composition for synthesizing a polyolefin, and a process for producing a polyolefin. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a transition metal compound, a catalyst composition for synthesizing polyolefins, and a process for producing polyolefins, and more particularly, to a process for producing a polyolefin, which can exhibit high reactivity with a newly synthesized transition metal compound, And more particularly, to a catalyst composition for polyolefin synthesis and a method for producing polyolefin which can easily control characteristics such as chemical structure, molecular weight distribution and mechanical properties of polyolefin.

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Since the Ziegler-Natta catalyst has a high activity, it has a wide molecular weight distribution of the resulting polymer because it is a multi- The composition distribution of the monomers is not uniform and there is a limit in ensuring desired physical properties.

Recently, a metallocene catalyst in which a transition metal such as titanium, zirconium, or hafnium and a ligand containing a cyclopentadiene functional group are bonded has been developed and widely used. These metallocene catalysts are single active site catalysts having one kind of active site. The molecular weight distribution of the produced polymer is narrow and the molecular weight, stereoregularity, crystallinity, especially reactivity of the comonomer can be greatly controlled depending on the structure of the catalyst and the ligand There is an advantage. However, the polyolefin polymerized with the metallocene catalyst has a narrow molecular weight distribution, and when it is applied to some products, productivity is remarkably decreased due to the influence of extrusion load, etc., and it is difficult to apply it to the field.

[Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, CGC) developed by DOW in the early 1990s compared with the previously known metallocene catalysts in the copolymerization reaction of ethylene and α- ) Is superior in that it can produce a polymer of high molecular weight while exhibiting high activity even at a high polymerization temperature, and (2) can easily synthesize an alpha-olefin having a large steric hindrance such as 1-hexene and 1-octene.

As various characteristics of CGC have become increasingly known, various attempts have been actively made to synthesize their derivatives and use them as polymerization catalysts. For example, instead of the silicon bridge, various other bridges and metal compounds into which a nitrogen substituent has been introduced have been synthesized, and the synthesis of polyolefins has been attempted. Representative metal compounds known until recently are as follows.

1

2

3

4

One

2

3

4

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, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and synthesis of polyolefins using the compounds was also partially tried. The examples are summarized as follows.

5

6

7

8

5

6

7

8

Also, the synthesis of the catalyst (8) having a structure similar to the above compound by Sumitomo Co., Ltd. and the high temperature high-pressure polymerization method using the catalyst (8) have been introduced.

9

9

On the other hand, in Mitsui, Japan, a transition metal compound (Ti, Zr) having a basic skeleton of phenoxyimine was developed to synthesize polyethylene and polypropylene having various properties. The characteristic feature of the catalyst is that it does not include a cyclopentadiene ligand which is an important skeleton of a conventional metallocene catalyst or CGC. As a result, these catalysts began to receive the spotlight as a next-generation catalyst that deviates from the post metallocene structure, ie, the metallocene structure. This catalyst was named as FI catalyst (10), and the activity and efficiency of the catalyst were investigated as various substituents were changed around the basic structure of the catalyst, and various studies related thereto were conducted.

10

10

Recently, a catalyst (11, 12) having another bridge, that is, a ligand in which a phenyl group is introduced, was introduced from CGC backbone by LG Chem (Organometallics, 2006, 25, 5122 and 2008, 27, 3907). These catalysts are characterized by exhibiting an activity equivalent to or higher than that of existing CGCs, a content of 1-octene and a molecular weight distribution in the synthesis of an ethylene / 1-octene copolymer.

11

12

11

12

However, the post metallocene catalyst that can be actually applied to commercial processes is not well known, and accordingly, a post metallocene catalyst capable of realizing higher polymerization performance and capable of providing a polyolefin having excellent physical properties Catalyst studies are still needed.

The present invention is to provide a novelly synthesized transition metal compound.

The present invention also provides a catalyst composition for polyolefin synthesis which can exhibit high reactivity in the polyolefin polymerization reaction and can easily control the characteristics such as the chemical structure, the molecular weight distribution, and the mechanical properties of the synthesized polyolefin .

The present invention also provides a process for producing a polyolefin which can more easily and stably synthesize an ethylene / alpha-olefin copolymer with a high selectivity and a reaction activity.

In the present specification, a transition metal compound represented by the following general formula (1) is provided.

[Chemical Formula 1]

In Formula 1, R ₁ is an aryl group (aryl) C 1 -C 10 alkyl group, or at least an alkyl group of straight or branched chain C 1 -C 51 substituted or unsubstituted C 6 -C 22 ring, R ₂ is An aryl group having 6 to 22 carbon atoms in which at least one of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted and R ₃ is a straight or branched alkenyl group having 2 to 12 carbon atoms , M ₁ is a transition metal of Groups 3 to 12, R ₄ and R ₅ are each a linear or branched alkyl or halogen group having 1 to 10 carbon atoms, R ₆ , R ₇ and R ₈ are each hydrogen, A straight chain or branched chain alkyl group having 1 to 10 carbon atoms, or a halogen group, and in the above formula, → denotes a coordinate bond.

Further, the present invention provides a catalyst composition for synthesizing polyolefin, which comprises the transition metal compound of the above formula (1).

In addition, the present invention provides a process for producing a polyolefin comprising the step of polymerizing ethylene in the presence of the catalyst for synthesizing polyolefin.

Hereinafter, a transition metal compound, a catalyst composition for synthesizing polyolefin, and a process for producing a polyolefin according to a specific embodiment of the present invention will be described in detail.

As used herein, Alkyl refers to a monovalent functional group derived from an alkane, alkenyl refers to a monovalent functional group derived from an alkene, quot; means a monovalent functional group derived from arene.

According to one embodiment of the invention, the transition metal compound of the above formula (1) may be provided.

The present inventors have newly synthesized a transition metal compound represented by the above formula (1). The transition metal compound represented by the above formula (1) has electronic and steric structures and the like, so that the polyolefin can easily control the characteristics such as chemical structure, molecular weight distribution, And the high reaction efficiency can be achieved through experiments.

In particular, the transition metal compound of the above formula (1) can oligomerize monomers such as ethylene due to its electronic and steric structure, and can easily oligomerize ethylene or a low-density polyethylene or an alpha-olefin in a single reactor have.

R ₁ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 22 carbon atoms in which at least one of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted, And R ₁ may be an aryl group having 6 to 14 carbon atoms in which one or more of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted.

The R ₂ may be an aryl group having 6 to 22 carbon atoms in which at least one of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted, and R ₂ is a linear chain having 1 to 5 carbon atoms Or an aryl group having 6 to 10 carbon atoms in which one or more branched-chain alkyl groups are substituted.

Further, R ₃ may be an alkenyl group (alkenyl) straight or branched chain having 2 to 12 carbon atoms, may also be in the R ₃ is an alkenyl group (alkenyl) straight or branched chain having 3 to 8 carbon atoms.

The M ₁ may be a transition metal of group 3 to 12, and specifically M ₁ may be cobalt.

Each of R ₄ and R ₅ may be a linear or branched alkyl group having 1 to 10 carbon atoms or a halogen group, and R ₄ and R ₅ may each be a halogen group.

Each of R ₆ , R ₇ and R ₈ is hydrogen, a linear or branched alkyl group having 1 to 10 carbon atoms, or a halogen group, and each of R ₆ , R ₇ and R ₈ is hydrogen or an alkyl group having 1 to 3 carbon atoms And may be a linear or branched alkyl group.

According to another embodiment of the present invention, there is provided a catalyst composition for synthesizing a polyolefin comprising the transition metal compound of the above formula (1).

As described above, the polyolefin can easily control characteristics such as chemical structure, molecular weight distribution, mechanical properties, and the like, and realize high reaction efficiency owing to the electronic and steric structure possessed by the transition metal compound of Formula 1. In addition, the transition metal compound of the above formula (1) can oligomerize monomers such as ethylene easily and efficiently due to its electronic and steric structure, and it is possible to synthesize low density polyethylene or alpha-olefin in one reactor with ethylene alone have.

Accordingly, in the case of using other transition metal compounds together with the transition metal compound of Formula 1, even when ethylene alone is used as the monomer, the ethylene / alpha-olefin copolymer can be synthesized with high selectivity and efficiency through one reaction process .

The catalyst composition for synthesizing polyolefins may further include a cocatalyst in addition to the transition metal compound represented by the above formula (1). The cocatalyst may comprise a compound of the following general formulas (11) to (13) or a mixture of two or more thereof.

 (11)

^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -

In Formula 11, L is a neutral or cationic Lewis base, [LH] + or [L] ⁺ is a Bronsted acid, H is a hydrogen atom, Z is a Group 13 element (preferably boron or aluminum in +3 type oxidation state) And at least one hydrogen atom is independently an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy functional group or phenoxy functional group. The 'hydrocarbyl' is a monovalent functional group in which a hydrogen atom is removed from a hydrocarbyl, and may include ethyl, phenyl, and the like.

[Chemical Formula 12]

D (R ₉ ) ₃

In Formula 12, D is aluminum or boron, R ₉ may be the same or different from each other, and each independently halogen; A hydrocarbon group of 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms substituted with halogen.

[Chemical Formula 13]

In Formula 13, R ₁₀ , R ₁₁ And R ₁₂ may be the same or different from each other and are each hydrogen; A halogen group; An aliphatic hydrocarbon group having 1 to 20 carbon atoms; Or an aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with halogen, and a is an integer of 2 or more.

The compound of Formula 11 may have a role of activating the transition metal compound of Chemical Formula 1 and may include a non-coordinating anion compatible with a cation which is a Bronsted acid. Preferred 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, anion-containing salts containing coordination complex compounds containing a single boron atom are preferred.

In the transition metal catalyst composition, the number of moles of the transition metal compound represented by Formula 1 may be 1: 1 to 1:10, preferably 1:10 to 1: 4. When the molar ratio is less than 1: 1, the amount of the cocatalyst is relatively small, so that the activation of the metal compound is not completely performed, so that the activity of the transition metal catalyst may not be sufficient. When the molar ratio is more than 1:10, The activity may be increased, but the use of unnecessarily cocatalyst may cause a problem of a large increase in production cost.

Specific examples of the compound of Formula 11 include triethylammoniumtetra (phenyl) boron, tributylammoniumtetra (phenyl) boron, trimethylammoniumtetra (phenyl) boron, tripropylammoniumtetra (phenyl) (P-tolyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl (Phenyl) boron, N, N-diethylamidinium tetra (phenyl) boron, N, N-diethylanilinium tetra (Pentafluorophenyl) boron, diethylammoniumtetra (pentafluorophenyl) boron, triphenylphosphonium tetra (phenyl) boron, trimethylphosphonium tetra (phenyl) boron, triethylammonium Tetra (phenyl) aluminum, tributylammonium (P-tolyl) aluminum, trimethylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (phenyl) aluminum, trimethylammonium tetra Aluminum triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) aluminum, tributylammoniumtetra N, N-diethylaniliniumtetra (phenyl) aluminum, N, N-diethylaniliniumtetra (phenyl) aluminum, N, N-diethylaniliniumtetra (pentafluoro (Phenyl) aluminum, trimethylphosphonium tetra (phenyl) aluminum, triethylammoniumtetra (phenyl) aluminum, diethylammoniumtetra (pentafluorophenyl) aluminum, triphenylphosphonium tetra (Phenyl) boron, trimethylammoniumtetra (phenyl) boron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra (p-tolyl) (O, p-dimethylphenyl) boron, tributylammoniumtetra (p-dimethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammoniumtetra (pentafluorophenyl) boron, N, N-diethylaniliniumtetra (phenyl) boron, N, N-diethylaniliniumtetra ) Boron, N, N-diethylaniliniumtetra (pentafluorophenyl) boron, diethylammoniumtetra (pentafluorophenyl) boron, triphenylphosphonium tetra (phenyl) boron, triphenylcarboniumtetra (p-tribromonomethylphenyl) boron, triphenylcarbonium tetra (pent Tetrafluorophenyl) boron, and trityltetra (pentafluorophenyl) boron, but are not limited thereto.

Meanwhile, the compound of formula (12) or (13) may serve as a scavenger for removing poison-acting impurities from the reactants.

In the transition metal catalyst composition, the number of moles of the transition metal compound represented by Formula 1 may be 1: 1 to 1: 8,000, preferably 1:10 to 1: 5,000. If the molar ratio is less than 1: 1, the effect of addition of the scavenger is insignificant. If the molar ratio exceeds 1: 5,000, the excess alkyl group or the like remaining in the reaction can not participate in the reaction, The side reaction may proceed and excess aluminum or boron may remain in the polymer.

Specific examples of the compound of formula (12) include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and preferably trimethylaluminum, triethylaluminum or triisobutylaluminum.

Specific examples of the compound of the above formula (13) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, preferably methyl aluminoxane.

The catalyst composition for synthesizing polyolefins may further include 50 to 1000 parts by weight of an organic solvent based on 100 parts by weight of the transition metal compound of Formula 1.

Examples of the organic solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene, xylene and benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. However, the solvent is not limited thereto. Solvents known to be usable for the transition metal catalyst may be used without limitation. The content of the organic solvent in the catalyst composition for polyolefin synthesis can be appropriately controlled according to the characteristics of the catalyst composition to be used and the conditions of the polyolefin production process to be used.

The catalyst composition for polyolefin synthesis may further comprise a carrier to which an effective component of the catalyst is fixed.

The transition metal compound of Formula 1 or the cocatalyst may be used in a state of being fixed to a carrier. The carrier may be used without limitation, as long as it is known to be commonly used in a catalyst for producing polyolefins. For example, Silica, alumina, magnesia, or a mixture thereof may be used. In addition, the carrier may be one that has been dried at elevated temperatures, and these may typically include oxides, carbonates, sulfates, nitrate components such as Na2O, K2CO3, BaSO4 and Mg (NO3) 2.

Meanwhile, the catalyst composition for polyolefin synthesis may further include a transition metal compound for synthesizing an ethylene / alpha -olefin copolymer containing a Group 4 transition metal.

The transition metal compound for synthesizing the ethylene /? - olefin copolymer can be used without limitation as long as it is a compound containing a Group 4 transition metal and known to be capable of copolymerizing ethylene and? -Olefin monomers (oligomers).

As described above, when the transition metal compound of Formula 1 is used, the oligomerization reaction can proceed at a high selectivity and yield even in the case of synthesizing by using only ethylene. Thus, the synthesis of the ethylene / alpha -olefin copolymer When the transition metal compound is further used, the ethylene / alpha -olefin copolymer can be formed with high efficiency.

Specific examples of the transition metal compound for synthesizing the ethylene /? - olefin copolymer include a transition metal compound represented by the following formula (2).

(2)

In Formula 2, R < ₁₁ > And R ₂₁ are each a straight or branched alkyl group having 1 to 5 carbon atoms and R _{12 ,} R ₂₂ , R ₁₄ , R ₁₅ , R ₂₄ and R ₂₅ are each a straight or branched alkyl group having 1 to 5 carbon atoms, R ₁₃ and R ₂₃ is an alkyl group of straight or branched chain having 1 to 10 carbon atoms, respectively, R ₅ is an alkyl group of straight or branched chain having 1 to 20, n is to 1 as the number of the R ₅ being substituted on the benzene ring Lt; / RTI >

In Formula 2, R < ₁₁ > And R ₂₁ are each a linear or branched alkyl group having 1 to 3 carbon atoms and R _{12 ,} R ₂₂ , R ₁₄ , R ₁₅ , R ₂₄ and R ₂₅ are each a straight or branched alkyl group having 1 to 3 carbon atoms, R ₁₃ and R ₂₃ are each a straight or branched alkyl group having 3 to 8 carbon atoms, R ₅ is a linear or branched alkyl group having 3 to 15 carbon atoms, and n is 2.

On the other hand, according to another embodiment of the present invention, there can be provided a process for producing a polyolefin comprising the step of polymerizing ethylene in the presence of the above-mentioned catalyst composition for polyolefin synthesis.

As described above, the transition metal compound of Formula 1 can easily control the electronic and stereoscopic environment around the metal, thereby increasing the yield of the polymerization reaction and improving the chemical structure, molecular weight distribution, and mechanical properties of the polyolefin Can be easily controlled.

By the method for producing the polyolefin, an olefin homopolymer, an olefin copolymer or an ethylene /? - olefin copolymer can be provided.

The polymerization of ethylene can be carried out at a temperature of 20 ° C or higher, or 25 ° C to 200 ° C, preferably 30 ° C to 100 ° C.

The polymerization of the ethylene monomer may be carried out in a continuous flow polymerization process, a bulk polymerization process, a suspension polymerization process, or an emulsion polymerization process, but preferably a solution polymerization reaction in a single reactor.

There is no particular limitation on the reactor used in the above production method, but it is preferable to use a continuous stirred tank reactor (CSTR) or a continuous flow reactor (PFR). In the above production process, it is preferable that two or more reactors are arranged in series or in parallel, and it is preferable that the separator further comprises a separator for continuously separating the solvent and unreacted monomers from the reaction mixture.

When the process for producing the polyolefin is carried out by 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.

In the process for producing the polyolefin, except for the above-mentioned contents, apparatuses, apparatuses, synthesis methods, reaction conditions, and the like known to be usable for synthesizing polyolefins using a metallocene catalyst can be used without any particular limitation.

According to the present invention, it is possible to provide a novel polyolefin composition which can exhibit high reactivity in the polyolefin polymerization reaction and can easily control the characteristics such as the chemical structure, molecular weight distribution and mechanical properties of the synthesized polyolefin, A catalyst composition for synthesis and a method for producing a polyolefin may be provided.

1 shows ¹ H-NMR data of a cobalt (II) chloride diamine catalyst (A) synthesized in Example 1.
2 shows ¹ H-NMR data of 6- (2-naphthyl) -pyridinyl-2-carbaldehyde (A2) synthesized in Example 1.
FIG. 3 shows ¹ H-NMR data of [6- (2-naphthyl) -pyridinyl] -5-hexen-1-ol (A3) synthesized in Example 1.
4 shows ¹ H-NMR data of [6- (2-naphthyl) -pyridinyl] -5-hexen-1-one (A4) synthesized in Example 1.
Fig. 5 shows ¹ H-NMR data of the zinc dichloride complex (A5-ZnCl ₂ ) synthesized in Example 1. Fig.
6 shows ¹ H-NMR data of the 6-naphthylpyridine diamine ligand (A5) synthesized in Example 1. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example 1 : Synthesis of transition metal catalyst]

The cobalt (II) chloride diimine catalyst of A was synthesized through the reaction shown in Scheme 1 below.

< Scheme 1 >

(1) 6- (2- Naphthyl ) - Pyridinyl -2- Of the carbaldehyde (A2)  synthesis

(2-naphthyl) -pyridinyl-2-carboxaldehyde was obtained from 6-bromo-pyridine-2-carbaldehyde (A1) via Suzuki reaction using a palladium complex substituted with aryl bromic acid and aryl group Aldehyde (A2) was synthesized (reaction yield: 80%).

IR analysis showed a peak near 1712 cm ^-1 , and ¹ H-NMR data of the synthesized 6- (2-naphthyl) -pyridinyl-2-carbaldehyde (A2) is shown in FIG.

(2) Synthesis of [6- (2- Naphthyl ) - Pyridinyl ] -5- Hexen (A3) &lt; / RTI &gt;

Bromo-1-pentyne is reacted with 6- (2-naphthyl) -pyridinyl-2-carbaldehyde (A2) in the presence of magnesium and THF to give the aldehyde group as racemic [6- (2-Naphthyl) -pyridinyl] -5-hexen-1-ol (A3) was synthesized via racemic allylation aldehyde.

IR analysis showed a peak near 3400 cm ^-1 and ¹ H-NMR data of the synthesized [6- (2-naphthyl) -pyridinyl] -5-hexen-1-ol (A3) Respectively.

(3) [6- (2- Naphthyl ) - Pyridinyl ] -5- Hexen (A4) &lt; / RTI &gt;

As shown in the above general formula 1, the synthesized [6- (2-naphthyl) -pyridinyl] -5-hexen-1-ol (A3) was oxidized using Dess-Martin periodinane (DMP) - (2-naphthyl) -pyridinyl] -5-hexen-1-one (A4) was synthesized (reaction yield: 98%).

IR analysis showed that the peak near 3400 ㎝ ^-1 disappeared and the peak near 1690 ㎝ ^-1 . ¹ H-NMR data of the synthesized [6- (2-naphthyl) -pyridinyl] -5-hexen-1-one (A4) is shown in FIG.

(4) Zinc dichloride Complex (A5-ZnCl ₂ )of  synthesis

As shown in the above general formula (1), in the presence of zinc dichloride (ZnCl ₂ ) and glacial acetic acid, the synthesized [6- (2-naphthyl) -pyridinyl] -5- to (A4) and diisopropylaniline 2: by reacting a weight ratio of 1, the zinc dichloride complex of the yellow solid (A5- ZnCl ₂₎ was formed (yield: 60%).

The ¹ H-NMR data of the synthesized zinc dichloride complex (A5-ZnCl ₂ ) is shown in FIG.

(5) 6- Naphthyl Pyridine dimine Of the ligand A5  synthesis

As shown in the above general formula 1, the synthesized dichloride zinc complex (A5- ZnCl ₂₎ by a carbon dioxide dihydrochloride solution (CH ₂ Cl ₂₎ was later, oxalic acid potassium (potassium oxalate) reaction solution and dissolved in 6-naphthyl (A5) was synthesized.

As a result of IR analysis, a peak near 1636 cm ^-1 was confirmed, and ¹ H-NMR data of the synthesized 6-naphthylpyridine diamine ligand (A5) is shown in FIG.

(6) Cobalt II ) Chloride Diimine  Synthesis of Catalyst (A)

As shown in the above general formula 1, a cobalt (II) chloride diimine catalyst (A) was synthesized by reacting a 6-naphthylpyridine diamine ligand (A5) with a THF solution of cobalt (II) chloride (reaction yield: 90 %)

IR analysis of the vicinity of a peak 1636 ㎝ ^-1 1630 ㎝ ^- was moved to the ^first point is been identified, showing the ¹ H-NMR data of the synthesized cobalt (II) chloride di-imine catalysts (A) in FIG.

[ Example 2 : Synthesis of ethylene /? - olefin copolymer]

(1) Preparation of catalyst composition for polyolefin synthesis

The cobalt (II) chloride diamine catalyst (A) obtained in Example 1 and the transition metal catalyst of the following formula (2-1) were mixed in a toluene solvent at a weight ratio of 1: 1, and methylaluminoxane as a co- 1, to prepare a catalyst composition for polyolefin synthesis.

[Formula 2-1]

In Formula 2-1, R ₁ , R ₂ and R ₄ are each a methyl group, R ₃ is a tert-butyl group, and R ₅ is an octyl group (-C ₈ H ₁₇ ).

(2) Synthesis of ethylene /? - olefin copolymer

The polymerization reaction was carried out at a temperature of about 30 캜 while injecting ethylene into the obtained catalyst composition for synthesizing polyolefin at a pressure of 1 atm for 30 minutes, and the reaction results were measured and shown in Table 1.

[Al] / [Ti]
<mol / mol> The concentration of [Ti]
<Μmol / L> Activity
(Activity) Mn (* 10 ⁴ ) Melting point (Tm)
<° C> Concentration of [1-Butene]
[mol%] 4000 10 360 12.4 121.39 19.58 20 140 25.3 121.37 24.03 30 113.3 34.9 121.39 22.54 2000 20 340 14.2 121.38 24.03

- unit of the activity: Kg-polymer * mol ^-1 * h ^-1

- The melting point was measured by DSC analysis.

The concentration of 1-butene in the synthesized ethylene / 1-butene copolymer was analyzed by ¹ H-NMR spectroscopy.

As shown in Table 1, when the catalyst composition comprising the cobalt (II) chloride diimine catalyst (A) synthesized in Example 1 and the transition metal compound represented by the general formula (2-1) was used, only ethylene was used as the monomer It was confirmed that an ethylene / 1-butene copolymer can be synthesized with high selectivity and efficiency through a single reaction process.

Claims (12)

A transition metal compound represented by the following formula (1); And
A transition metal compound for the synthesis of a copolymer between ethylene and an? -Olefin comprising a Group 4 transition metal;
[Chemical Formula 1]

In Formula 1,
R ₁ is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 22 carbon atoms in which at least one of linear or branched alkyl groups having 1 to 5 carbon atoms is substituted or unsubstituted,
R ₂ is an aryl group having 6 to 22 carbon atoms in which at least one of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted,
R ₃ is a linear or branched alkenyl group having 2 to 12 carbon atoms,
M ₁ is a transition metal of Groups 3 to 12,
R ₄ and R ₅ are each a linear or branched alkyl group having 1 to 10 carbon atoms or a halogen group,
R ₆ , R ₇ and R ₈ are each hydrogen, a straight or branched alkyl group having 1 to 10 carbon atoms, or a halogen group,
In the above formula, → denotes coordination bonding.
The method according to claim 1,
In Formula 1,
R ₁ is an aryl group having 6 to 14 carbon atoms in which at least one of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted or unsubstituted,
R ₂ is an aryl group having 6 to 10 carbon atoms in which at least one of a linear or branched alkyl group having 1 to 5 carbon atoms is substituted,
R ₃ is a linear or branched alkenyl group having 3 to 8 carbon atoms,
R ₄ and R ₅ are each a halogen group,
M ₁ is cobalt,
R ₆ , R ₇ and R ₈ are each hydrogen or a straight or branched alkyl group having 1 to 3 carbon atoms,
Catalyst composition for polyolefin synthesis.
delete The method according to claim 1,
5. The catalyst composition for polyolefin synthesis according to claim 1, further comprising a cocatalyst.
5. The method of claim 4,
Wherein the cocatalyst is at least one selected from the group consisting of compounds represented by the following formulas (11) to (13):
(11)
^{[LH] + [Z (E} ) 4] - or ^{[L] + [Z (E} ) 4] -
In Formula 11,
L is a neutral or cationic Lewis base,
[LH] + or [L] ⁺ is a Bronsted acid,
H is a hydrogen atom,
Z is a Group 13 element,
E may be the same or different from each other, and independently at least one hydrogen atom is replaced by an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy functional group or phenoxy functional group, Lt; / RTI &gt;
[Chemical Formula 12]
D (R ₉ ) ₃
In Formula 12,
D is aluminum or boron,
R ₉ may be the same or different from each other and are each independently halogen; A hydrocarbon group of 1 to 20 carbon atoms; Or a hydrocarbon group of 1 to 20 carbon atoms substituted with halogen,
[Chemical Formula 13]

In Formula 13, R ₁₀ , R ₁₁ And R ₁₂ may be the same or different from each other and are each hydrogen; A halogen group; An aliphatic hydrocarbon group having 1 to 20 carbon atoms; Or an aliphatic hydrocarbon group having 1 to 20 carbon atoms substituted with halogen, and a is an integer of 2 or more.
6. The method of claim 5,
Wherein the number of moles of the transition metal compound represented by Formula 1 is 1: 1 to 1:10.
6. The method of claim 5,
Wherein the number of moles of the transition metal compound represented by Formula 1 is 1: 1 to 1: 8,000.
The method according to claim 1,
The catalyst composition for synthesizing polyolefin according to claim 1, further comprising 50 to 1000 parts by weight of an organic solvent based on 100 parts by weight of the transition metal compound of the formula (1).
The method according to claim 1,
A catalyst composition for polyolefin synthesis, further comprising a carrier to which an effective component of the catalyst is fixed.
delete The method according to claim 1,
Wherein the transition metal compound for synthesizing a copolymer between ethylene and an? -Olefin comprises a compound represented by the following formula (2):
(2)

In Formula 2,
R ₁₁ and R ₂₁ are each a straight or branched alkyl group having 1 to 5 carbon atoms,
R _12, R ₂₂ , R ₁₄ , R ₁₅ , R ₂₄ and R ₂₅ are each a straight or branched alkyl group having 1 to 5 carbon atoms,
R ₁₃ and R ₂₃ are each a straight or branched alkyl group having 1 to 10 carbon atoms,
R ₅ is a linear or branched alkyl group having 1 to 20 carbon atoms,
n is an integer of 1 to 4 as the number of R ₅ substituted on the benzene ring.
A process for producing a polyolefin comprising the step of polymerizing ethylene in the presence of the catalyst composition for polyolefin synthesis according to claim 1.

Images