KR20150016830A - Method for preparing of novel ligand compound and transiton metal compound - Google Patents

Method for preparing of novel ligand compound and transiton metal compound Download PDF

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KR20150016830A
KR20150016830A KR1020130092764A KR20130092764A KR20150016830A KR 20150016830 A KR20150016830 A KR 20150016830A KR 1020130092764 A KR1020130092764 A KR 1020130092764A KR 20130092764 A KR20130092764 A KR 20130092764A KR 20150016830 A KR20150016830 A KR 20150016830A
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carbon atoms
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alkyl group
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김슬기
한기원
장재권
한효정
이은정
이충훈
박인성
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
    • C08F4/16—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of silicon, germanium, tin, lead, titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof

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Abstract

The present invention relates to a novel ligand compound and a method for producing a transition metal compound, and the ligand compound and the transition metal compound can be used for producing a polyolefin having a high melting point and excellent heat resistance.

Description

METHOD FOR PREPARING NOVEL LIGAND COMPOUND AND TRANSITON METAL COMPOUND BACKGROUND OF THE INVENTION 1. Field of the Invention [0001]

The present invention relates to a novel ligand compound and a method for producing a transition metal compound, and more particularly, to a novel ligand compound and a method for producing a transition metal compound capable of providing a polyolefin having a high melting point and excellent heat resistance .

Ziegler-Natta catalysts of titanium or vanadium compounds have been widely used for the commercial production of polyolefins. Although the Ziegler-Natta catalysts have high activity, they have a wide molecular weight distribution of the produced polymers because of their high activity, The uniformity of the composition 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. The metallocene compound is generally activated by using aluminoxane, borane, borate or other activator. For example, a metallocene compound having a ligand containing a cyclopentadienyl group and two sigma chloride ligands uses aluminoxane as an activator. 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 limitation in that it is generally difficult to apply the polyolefin to a product because the melting point of the polyolefin is lower than that of the Ziegler-Natta catalyst. Thus, there have been many attempts to improve the heat resistance of the related polyolefin.

Particularly, in order to solve the problems of the metallocene catalyst described above, many transition metal compounds in which a ligand compound containing a hetero atom is coordinated have been introduced. Specific examples of such a heteroatom-containing transition metal compound include azaferrocene compound having a cyclopentadienyl group containing a nitrogen atom, a structure in which a functional group such as a dialkylamine is connected to a cyclopentadienyl group as an additional chain Or a titanium (lV) metallocene compound into which a cyclic alkylamine functional group such as piperidine is introduced, and the like.

Among all these attempts, however, only a few metallocene catalysts have been applied to commercial plants, and thus can be used as polymerization catalysts capable of providing higher polymerization performance and providing polyolefins with excellent physical properties Research on possible metallocene compounds is still needed.

The present invention is to provide a novel method for producing a ligand compound capable of providing a polyolefin having a high melting point and excellent heat resistance.

The present invention also provides a process for producing a transition metal compound capable of providing a polyolefin having a high melting point and excellent heat resistance.

The present invention provides a process for producing a ligand compound represented by the following general formula (1).

The present invention also provides a process for producing a transition metal compound represented by the following general formula (2).

Hereinafter, a method for preparing a ligand compound and a transition metal compound according to a specific embodiment of the present invention will be described in detail.

According to an embodiment of the present invention, there is provided a process for preparing a compound represented by the following formula (5) by reacting a compound represented by the following formula (3) with a compound represented by the following formula (4) And reacting a compound represented by the following formula (5) or a lithium salt thereof with a compound represented by the following formula (6): < EMI ID = 1.0 >

(3)

Figure pat00001

[Chemical Formula 4]

Figure pat00002

[Chemical Formula 5]

Figure pat00003

[Chemical Formula 6]

(R 10 ) 2 QX 2

(7)

Figure pat00004

 [Chemical Formula 1]

Figure pat00005

In the above formulas (1) and (3) to (6)

R 1 to R 8 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms , An arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, and a silyl group, or R 1 to R 9 Two or more of which are adjacent to each other may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring.

The R 9 may be hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The Q may be carbon or silicon.

X 1 , X 2 , X 3, and X 4 may be hydrogen, a halogen group, or an alkyl group having 1 to 20 carbon atoms.

The inventors of the present invention have found that by virtue of the inherent chemical structure of the ligand compound of Formula 1, the electronic / stereoscopic environment around the transition metal that can be bonded thereto can be easily controlled, and the melting point and stereoregularity of the synthesized polyolefin It is possible to provide a transition metal catalyst capable of easily controlling the characteristics of the catalyst.

In particular, the ligand compound of formula (1) comprises two indenyl groups connected to an acridine group, and the two indenyl groups have a C2 symmetrical crosslinked structure connected by a silicon or carbon bridge. The steric bulkiness The acrolein group having a large electron density and a high electron density can control the stereoregularity of the polyolefin produced in the olefin polymerization, and thus a polyolefin having a high melting point can be produced.

Each of the substituents defined in the above Formulas 1 and 3 to 6 will be described as follows.

The alkyl group having 1 to 20 carbon atoms may include a linear or branched alkyl group, and the alkenyl group having 2 to 20 carbon atoms may include a straight chain or branched alkenyl group.

The aryl group is preferably an aromatic ring having 6 to 20 carbon atoms. Specific examples thereof include phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, and anisole. However, the aryl group is not limited thereto.

The alkylamino group refers to an amino group to which one or more straight or branched alkyl groups having 1 to 20 carbon atoms are introduced, and specifically includes, but is not limited to, dimethylamino group, diethylamino group, and the like.

The arylamino group refers to an amino group having at least one aryl group having 6 to 20 carbon atoms introduced thereto, and specifically includes, but is not limited to, a diphenylamino group and the like.

The halogen group means fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

The silyl group may include a silyl functional group introduced with an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, Specific examples thereof include trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris (trimethylsilyl) However, the present invention is not limited to these examples.

Each of R 1 to R 9 in Formula 1 is preferably independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

R 9 in Formula 1 may be hydrogen or an alkyl group having 1 to 20 carbon atoms.

In the method for preparing the ligand compound of the above embodiment, the compound represented by Formula 5 may be prepared by first reacting the compound represented by Formula 3 with the compound represented by Formula 4.

More specifically, the acridine compound represented by Formula 3 and the indenyl compound represented by Formula 4 may be coupled to form a C-N bond.

At this time, the reaction between the compound represented by Formula 3 and the compound represented by Formula 4 below may be carried out in the presence of palladium catalyst. The palladium catalyst is a compound containing palladium, available, but the catalyst is not particularly limited, and tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4), palladium chloride (PdCl 2), palladium acetate (Pd ( OAc) 2), bis (dibenzylideneacetone) palladium (Pd (dba) 2), Pd (tBu 3 P 2), and it may be more efficient to use a palladium catalyst such as, economically produce the compound represented by formula (5) It is preferable.

In addition, the step of preparing the compound represented by Formula 5 may further include a base. The base can effectively form a compound of the formula (5) by effectively mediating the reaction between the compound represented by the formula (3) and the compound represented by the formula (4), thereby reducing the reaction time .

Use The types of the base is not necessarily to be significantly limited, and specific examples tBuOLi, tribasic potassium (K 3 PO 4), potassium carbonate (K 2 CO 3), cesium carbonate (Cs 2 CO 3), potassium fluoride (KF ), Sodium fluoride (NaF), cesium fluoride (CsF), tetrabutylammonium fluoride (TBAF), or mixtures thereof.

Next, the ligand compound represented by Formula 1 can be obtained by reacting the compound represented by Formula 5 or its lithium salt with the compound represented by Formula 6. As described above, the lithium salt of the indenyl compound represented by Formula 5 may be prepared by reacting an indenyl compound with an organic lithium compound such as nBuLi.

More specifically, after the compound represented by the formula (5) or the lithium salt thereof is mixed with the compound represented by the formula (6), the mixture is reacted by stirring. Then, the reaction product is filtered to wash the resulting precipitate, and dried under reduced pressure to obtain a compound represented by the above-mentioned formula (1) wherein the indenyl derivative is a structure in which the compound represented by the formula (5) is cross- Lt; / RTI > can be obtained.

The mixing ratio of the rac: meso form of the ligand compound represented by the formula (1) may be 3: 1 to 1: 3. This is because the compound represented by Formula 5 and the compound represented by Formula 6 may be bonded in a racemic structure or may be bonded in a meso structure.

Meanwhile, the step of preparing the compound represented by the above formula (5) or (1) can be performed by applying the conventional organic synthesis conditions known in the art. For example, the reactants are mixed and reacted in a temperature range of -100 ° C to 300 ° C and a pressure range of 1 to 30 atmospheres, usually for about 24 hours until the reaction is completed, to obtain the compound represented by the above formula 5, 7 or 1 Can be manufactured.

At this time, preferred examples of the ligand compound represented by the formula (1) include compounds represented by the following formulas (11) to (14).

(11)

Figure pat00006

[Chemical Formula 12]

Figure pat00007

[Chemical Formula 13]

Figure pat00008

[Chemical Formula 14]

Figure pat00009

In the formulas (11) and (14), Me is a methyl group and Ph is a phenyl group.

According to another embodiment of the present invention, there is provided a process for preparing a transition metal compound represented by the following formula (2), comprising reacting a compound represented by the formula (1) or a lithium salt thereof with a compound represented by the following formula A method can be provided.

(2)

Figure pat00010

(7)

MX 4

In the above formulas 2 and 7,

R 1 to R 8 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms , An arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, and a silyl group, or two or more of R 1 to R 8, which are adjacent to each other, An alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring.

The R 9 may be hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The Q may be carbon or silicon.

The M may be a Group 4 transition metal.

X is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An alkylamino group, an arylamino group having 6 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms.

The present inventors have found that the electronic / stereoscopic environment around the transition metal can be easily controlled owing to the chemical structure of the transition metal compound of the above formula (2) in which a ligand compound of a specific structure is bonded to the transition metal, And stereoregularity of the transition metal catalyst can be easily controlled.

In particular, as described above, the transition metal compound represented by Formula 2 includes two indenyl groups connected to an acridine group, and the two indenyl groups include a ligand having a C2 symmetric cross-linked structure connected with a silicon or carbon bridge Wherein the acridine group having a high steric bulkiness and a low electron density has a stereoregularity of a polyolefin prepared in the olefin polymerization, the stereoregularity can be controlled and a polyolefin having a high melting point can be produced.

The transition metal of the fourth group defined as M may be Ti (titanium), Zr (zirconium), hafnium (Hf) or the like, but is not limited thereto.

Each of R 1 to R 9 in Formula 2 is preferably independently hydrogen, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 9 is preferably hydrogen or an aryl group having 6 to 20 carbon atoms Do.

R 10 in Formula 2 may be hydrogen or an alkyl group having 1 to 20 carbon atoms.

More specifically, the transition metal compound represented by Formula 2 may be prepared by mixing the ligand compound represented by Formula 1 or a lithium salt thereof and the metal compound represented by Formula 7, and reacting the mixture by stirring. Then, the reaction product is filtered to wash out the resulting precipitate, and dried under reduced pressure to obtain a transition metal compound represented by the general formula (2) in the form of a complex in which a transition metal atom is bonded to the ligand compound.

The ligand compound represented by the formula (1) may be used as a lithium salt by reacting with an organic lithium compound such as n-BuLi.

As described above, the ligand compound represented by Formula 1 may be a mixture of rac: meso at a ratio of 3: 1 to 1: 3, and may be prepared by reacting the compound represented by Formula 7 The transition metal compound represented by Formula 2 may also be mixed at a ratio of rac: meso of 3: 1 to 1: 3, preferably 2: 1 to 1: 2.

Meanwhile, the step of preparing the compound represented by the formula (2) may be carried out by applying conventional organic synthesis conditions known in the art. For example, the compound represented by the formula (1) and the compound represented by the formula (7) are mixed and reacted in a pressure range of -100 ° C to 300 ° C and 1 to 30 atm for about 24 hours until the reaction is completed, 2 can be prepared.

At this time, preferred examples of the ligand compound represented by the formula (2) include compounds represented by the following formulas (21) to (28).

[Chemical Formula 21]

Figure pat00011

[Chemical Formula 22]

Figure pat00012

(23)

Figure pat00013

≪ EMI ID =

Figure pat00014

(25)

Figure pat00015

(26)

Figure pat00016

(27)

Figure pat00017

(28)

Figure pat00018

In Formulas 21 to 28, Me is a methyl group and Ph is a phenyl group.

According to the present invention, a novel ligand compound capable of providing a polyolefin having a high melting point and excellent in heat resistance and a method for producing a transition metal compound can be provided.

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.

In the following Examples, Comparative Examples and Experimental Examples, organic reagents and solvents were purchased from Aldrich and Merck and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment. In addition, a spectrum was obtained using a 400 MHz nuclear magnetic resonance (NMR) to demonstrate the structure of the compound.

< Example : Ligand  Synthesis of Compound and Transition Metal Compound &gt;

Example 1  : rac - dimethylsilylene -(4-( acridine -10 (9H) - yl )-2- methyl -One H -inden-1-yl) (7- (acridin-10 (9H) -yl) -2-methyl- H -inden-1-yl) zirconium  Synthesis of dichloride

(1) the ligand (4- (acridin-10 (9H ) -yl) -2-methyl-1 H -inden-1-yl) (7- (acridin-10 (9H) -yl) -2-methyl-1 H -inden-1-yl) dimethyl silane

Figure pat00019

And then put into a Schlenk flask of 250mL 10- (2-methyl-1 H -inden-4-yl) -9,10-dihydroacridine (7.2g, 23.3mmol) was added to dry diethyl ether 116mL dissolve the starting material, -78 N-BuLi (2.5 M in n-Hx) (10.2 mL) was added thereto at room temperature, and the mixture was stirred overnight at room temperature and filtered using glass frit (G4). Then, the solid remaining in the glass frit was vacuum dried to obtain a lithiated product (7.6 g, 100% yield) of a white solid. In the glove box, the lithiated product (7.6 g, 23.3 mmol) was placed in a 250 mL Schlenk flask and dissolved in 66.5 mL of dry toluene and 3.3 mL of THF. The temperature was lowered to -30 ° C, dichlorodimethylsilane (1.4 mL, 11.6 mmol) was added, and the mixture was stirred at room temperature for 1 day. After completion of the reaction, 120 mL of deionized water was added to terminate the reaction.

The water and organic layers were separated and the aqueous layer was extracted twice with 120 mL of dichloromethane (DCM). The organic layer was dried with Na 2 CO 3 , filtered, distilled, and vacuum-dried at room temperature overnight to obtain a yellow solid ligand compound (7.63 g, quantitative yield relative to lithiated product, 99% yield relative to the starting material) . 1 H-NMR analysis showed that the racemic: meso ratio was about 1: 1.

1 H-NMR (CDCl 3) : δ7.86 ~ 6.44 (m, 44H in rac - and meso -isomers), 4.33 (m, 8H in rac - and meso -isomers), 4.10 ~ 3.90 (s, 4H in rac - and meso -isomers), 2.09 ( m, 6H in meso -isomer), 1.99 (s, 6H in rac -isomer), -0.13 ~ -0.23 (m, 12H in rac - and meso -isomers)

(2) Transition metal compound rac - dimethylsilylene -(4-( acridine -10 (9H) - yl ) -2-methyl-1 H -inden-1-yl) (7- (acridin-10 (9H) -yl) -2-methyl- H -inden-1-yl) zirconium dichloride

Figure pat00020

3.0 g (4.76 mmol, rac: meso = 1: 1) of the ligand compound prepared in the above (1) was added to a 100 mL Schlenk flask and 48 mL of dry diethyl ether was added to dissolve the starting material. Then, n-BuLi 2.5M in n-Hx) was added thereto, followed by stirring at room temperature for 1 day. Then, it was filtered using glass frit (G4). The solid remaining in the glass frit was vacuum dried to obtain a lithiated product (3.1 g, 95% yield) of a brown solid. In the glove box, the lithiated product (3.1 g, 4.5 mmol) was placed in a 250 mL Schlenk flask and dissolved in 50 mL of dry toluene. The mixture was cooled to -78 ° C and transferred to a Schlenk flask equipped with a pre-prepared Zirconium (Ⅳ) chloride (1.22 g) solution (5.2 mmol in 50 mL toluene) at -78 ° C using a cannula and stirred overnight at room temperature. After completion of the reaction, the solution was filtered with glass frit (G4) containing celite. The solid remaining in the glass frit was dissolved in 20 mL of dry toluene. The toluene solution was vacuum dried to obtain a red solid. It was dissolved in dry toluene and stored in a freezer at -30 ° C for 3 days for recrystallization. The resulting red solid was filtered with glass frit (G4) and dried in vacuo to give the final product. 1 H-NMR analysis showed that the racemic: meso ratio was about 1: 1.

1 H-NMR (CDCl 3) : δ7.55 ~ 6.56 (m, 48H in rac - and meso -isomers), 3.89 (s, 8H in rac - and meso -isomers), 1.84 ~ 1.78 (s, 12H in rac - and meso- isomers), 0.93-0.53 (m, 12H rac - and meso- isomers)

Example 2  : rac - dimethylsilylene -(4-( acridine -10 (9H) - yl )-2- methyl -One H -inden-1-yl) (7- (acridin-10 (9H) -yl) -2-methyl- H -inden-1-yl) hafnium dichloride  synthesis

Figure pat00021

A ligand compound and a transition metal compound were synthesized in the same manner as in Example 1, except that HfCl 4 was used instead of ZrCl 4 .

1 H-NMR (CDCl 3) : δ7.61 ~ 6.49 (m, 48H in rac - and meso -isomers), 3.89 (s, 8H in rac - and meso -isomers), 1.95 ~ 1.92 (d, 12H in rac - and meso -isomers), 0.95 ( s, 3H in meso -isomers), 0.73 (s, 6H in rac - isomers), 0.56 (s, 3H in meso -isomers)

< Comparative Example  >

Comparative Example 1 : rac -1,1 ' dimethylsilylene - bis ( indenyl ) hafnium dichloride Synthesis of

U.S. Pat. 5,905,162.

< Experimental Example  >

Experimental Example 1 : Preparation of propylene homopolymer

A toluene solvent (0.2 L) was added to a 300 mL minicable reactor, and the temperature of the reactor was preheated to 70 캜. 2 ml of a dimethylanilinium tetrakis (pentafluorophenyl) borate cosurfactant of 5 x 10 -3 M was introduced into the reactor through a syringe, and then the transition metal compound of Example 1 and Comparative Example 1 treated with triisobutyl aluminum compound 1 x 10 &lt; -3 &gt; M, 1 mL) was charged to the reactor. Polymerization was carried out by injecting 5 bar of propylene for 10 minutes. After the polymerization reaction was carried out for 10 minutes, the remaining gas was removed and the polymer solution was cooled by adding excess ethanol to induce precipitation. The obtained polymer was washed with ethanol and acetone two to three times, respectively, and dried in a vacuum oven at 80 캜 for 12 hours or more, and then the physical properties thereof were measured.

The physical properties of the propylene homopolymer prepared using the transition metal compounds prepared in the above Examples and Comparative Examples are shown in Table 1 below.

The melting point of the polymer was measured using Q100 from TA and obtained through a second melting with a temperature rise of 10 ° C per minute to eliminate the thermal history of the polymer.

 Catalyst (μmol) Catalytic activity (kg / mmol hr) Polymer weight (g) Melting point (캜) Example 1 1.0 37 6.2 153.7 Comparative Example 1 0.1 151 12.6 122.5

As shown in Table 1, the propylene polymer prepared using the catalyst of Example 1 had a higher melting point (T m ) than that of Comparative Example 1. From the above results, it can be seen that the propylene polymer has a higher melting point as the degree of stereoregularity is higher. Therefore, it can be confirmed that an olefin polymer having a high melting point and stereoregularity can be prepared when the transition metal compound of the above embodiment is used as a catalyst.

Claims (13)

Reacting a compound represented by the following formula (3) and a compound represented by the following formula (4) to prepare a compound represented by the following formula (5); And
Reacting a compound represented by the following formula (5) or a lithium salt thereof with a compound represented by the following formula (6): &lt; EMI ID =
(3)
Figure pat00022

[Chemical Formula 4]
Figure pat00023

[Chemical Formula 5]
Figure pat00024

[Chemical Formula 6]
(R 10 ) 2 Q (X 3 ) 2
[Chemical Formula 1]
Figure pat00025

In the above formulas (1) and (3) to (6)
R 1 to R 8 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms , An arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, and a silyl group,
Alternatively, two or more adjacent groups out of R 1 to R 8 may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring,
R 9 is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
Q is carbon or silicon,
X 1 , X 2 , X 3 and X 4 are hydrogen, a halogen group, or an alkyl group having 1 to 20 carbon atoms.
The method according to claim 1,
Wherein the step of preparing the compound represented by the formula (5) is carried out in the presence of a palladium catalyst.
3. The method of claim 2,
The palladium catalyst may be at least one selected from the group consisting of tetrakis (triphenylphosphine) palladium (Pd (PPh 3 ) 4 ), palladium chloride (PdCl 2 ), palladium acetate (Pd (OAc) 2 ), bis (dibenzylideneacetone) palladium dba) 2), and Pd (tBu 3 P 2) method of producing a ligand compound comprising at least one catalyst selected from the group consisting of.
The method according to claim 1,
Wherein the step of preparing the compound represented by the general formula (5) is carried out by further comprising a base.
The method according to claim 1,
Wherein R 1 to R 8 in Formula 1 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
The method according to claim 1,
Wherein R 9 in the formula (1) is hydrogen or an alkyl group having 1 to 20 carbon atoms.
The method according to claim 1,
Wherein the ligand compound represented by Formula 1 has a mixing ratio of rac: meso of from 3: 1 to 1: 3.
The method according to claim 1,
Wherein the compound represented by Formula 1 is a compound selected from the group consisting of compounds represented by Formulas 11 to 14:
(11)
Figure pat00026

[Chemical Formula 12]
Figure pat00027

[Chemical Formula 13]
Figure pat00028

[Chemical Formula 14]
Figure pat00029

In the formulas (11) and (14), Me is a methyl group and Ph is a phenyl group.
A process for producing a transition metal compound represented by the following formula (2), comprising reacting a compound represented by the formula (1) or a lithium salt thereof with a compound represented by the following formula (7)
(2)
Figure pat00030

(7)
MX 4
In the above formulas 2 and 7,
R 1 to R 8 each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms , An arylalkyl group having 7 to 20 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, and a silyl group,
Alternatively, two or more adjacent groups out of R 1 to R 8 may be linked to each other by an alkylidene group containing an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms to form a ring,
R 9 is hydrogen, a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,
Q is carbon or silicon,
M is a transition metal of Group 4,
X is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, An amino group, an arylamino group having 6 to 20 carbon atoms or an alkylidene group having 1 to 20 carbon atoms.
10. The method of claim 9,
Wherein M is selected from the group consisting of Ti, Zr and Hf.
10. The method of claim 9,
Wherein each of R 1 to R 8 in Formula 2 is independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
10. The method of claim 9,
Wherein R 9 in Formula 2 is hydrogen or an alkyl group having 1 to 20 carbon atoms.
10. The method of claim 9,
Wherein the transition metal compound represented by Formula 2 is represented by one of the following Chemical Formulas 21 to 28:
[Chemical Formula 21]
Figure pat00031

[Chemical Formula 22]
Figure pat00032

(23)
Figure pat00033

&Lt; EMI ID =

(25)
Figure pat00035

(26)
Figure pat00036

(27)
Figure pat00037

(28)
Figure pat00038

In Formulas 21 to 28, Me is a methyl group and Ph is a phenyl group.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10438992B2 (en) 2015-02-13 2019-10-08 Seoul Viosys Co., Ltd. Light-emitting element and light-emitting diode

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10438992B2 (en) 2015-02-13 2019-10-08 Seoul Viosys Co., Ltd. Light-emitting element and light-emitting diode
US11282892B2 (en) 2015-02-13 2022-03-22 Seoul Viosys Co., Ltd. Light-emitting element including intermediate connection and branches

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