KR102306523B1 - Method for preparing thiophene-fused cyclopentadienyl ligand and metallocene catalyst composition - Google Patents

Abstract

The present invention provides a method for preparing a thiophene-condensed ring cyclopentadienyl ligand and a methyllocene catalyst, which can be prepared at a relatively high temperature by using chloromethyl alkyl ether and can be efficiently separated using an organic acid do.

Description

Thiophene-condensed ring cyclopentadienyl ligand and method for preparing a metallocene catalyst composition

The present invention relates to a method for preparing a thiophene-condensed ring cyclopentadienyl ligand and a metallocene catalyst.

Since the homogeneous Ziegler catalyst in which a Group 4 metallocene compound was activated as a methylaluminoxane co-catalyst was published in the late 1970s, academia and industry have been using homogeneous catalysts of various structures to produce polyolefins having desired properties. did. Conventional heterogeneous catalysts have disadvantages in that the amount of alpha-olefins incorporated during ethylene/alpha-olefin copolymerization is small, and the alpha-olefins are incorporated only in chains with mainly small molecular weights.

On the other hand, when a homogeneous catalyst is used, there is an advantage in that the amount of alpha-olefin incorporated in the ethylene/alpha-olefin copolymerization is large, and the distribution of the alpha-olefin is uniformly displayed. However, compared to the case of using a heterogeneous catalyst, it is difficult to prepare a polymer having a high molecular weight.

If the molecular weight of the polymer is small, there are limitations in the development of uses, such as not being applicable to products requiring high strength. For this reason, the industry still manufactures a polymer using a conventional heterogeneous catalyst, and the homogeneous catalyst is limitedly used only for polymers of several grades.

In order to overcome the above limitation, the amido ligand and ortho-phenylene form a condensed ring, and the pentacyclic pi-ligand bonded to the ortho-phenylene is fused by a thiophene hetero ring. A technique for preparing a catalyst containing a transition metal compound having a ligand has been developed, and it has been reported that a high molecular weight polymer can be prepared as well as showing a higher activity than a catalyst in which a thiophene hetero ring is not fused.

A method for preparing the catalyst is known in the following literature (Dalton Trans., 2010, 39, 9994), and the catalyst is characterized in that it has a bridge at the ortho-phenylene position of a tetrahydroquinoline derivative. am. In order to introduce a bridge at the ortho-phenylene position, an amine group of the tetrahydroquinoline derivative is reacted with CO ₂ , and then the ortho position is selectively lithiated to introduce the bridge. A constrained-geometry catalyst (CGC) having a thiophene-condensed ring is prepared through a methylation step after metal complexing the ligand prepared according to the above method.

However, in preparing the ligand of the catalyst _{, a cryogenic temperature is required as CO 2} is used in the ortho-lithiation process, and in some cases during the purification process, the tetrahydroquinoline derivative starting material is precipitated together as a salt. A problem was found in that the purification efficiency was lowered.

Republic of Korea Patent Registration No. 10-0986301

Dalton Trans., 2010, 39, 9994

It is an object of the present invention to not require cryogenic reaction conditions when preparing a thiophene-condensed ring cyclopentadienyl ligand, to efficiently separate the ligand, and to prepare a thiophene-condensed thiophene-condensed ligand in a single reaction tank (one-pot). To provide a method for preparing a cyclic cyclopentadienyl ligand.

According to one embodiment of the present invention, (a) adding a lithium compound and chloromethyl alkyl ether to the tetrahydroquinoline derivative represented by the following formula (2) to form a compound represented by the following formula (3); (b) reacting the compound represented by the formula (3) with the lithium compound, and then adding a compound represented by the following formula (4); and (c) treating the mixture formed in step (b) with an organic acid to separate the thiophene-condensed ring cyclopentadienyl ligand represented by the following formula (1); A method for preparing a ligand is provided:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4, R ¹ to R ¹⁰ are the same as or different from each other, and each independently substituted or unsubstituted with hydrogen, an acetal group or an ether group (C ₁ -C ₂₀ ) Alkyl group, acetal group or ether group substituted or Unsubstituted (C ₂ -C ₂₀ ) Alkenyl group, acetal group or ether group unsubstituted or substituted (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, acetal group or ether group substituted or unsubstituted (C ₆ -C ₂₀ )aryl (C ₁ -C _{20 ) A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an alkyl group, an acetal group, or an ether group ^{; R 1} is ^{connected to R 2} to form a ring R ³ may ^{be connected to R 4} to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring; R ¹¹ to R ¹³ are the same as or different from each other and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ ) Alkyl group, an acetal group or an ether group (C ₂ -C ₂₀ ) alkenyl group, an acetal group or an ether A (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, an acetal group, or an ether group (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with a group (C 1 -C 20 ) , A (C ₁ -C ₂₀ )silyl group unsubstituted or substituted with an acetal group or an ether group, a (C ₁ -C ₂₀ )alkoxy group unsubstituted or substituted with an acetal group or an ether group, or substituted or unsubstituted with an acetal group or an ether group a cyclic (C ₆ -C ₂₀ )aryloxy group; R ¹¹ and R ¹² , or R ¹² and R ¹³ may be linked to each other to form a ring).

According to another embodiment of the present invention, (a) preparing a compound represented by the following formula (3) by adding a lithium compound and chloromethyl alkyl ether to the tetrahydroquinoline derivative represented by the following formula (2); (b) reacting the compound represented by the formula (3) with the lithium compound, and then adding a compound represented by the following formula (4); (c) treating the mixture formed in step (b) with an organic acid to isolate a thiophene-condensed cyclic cyclopentadienyl ligand represented by the following formula (1); and (d) treating the thiophene-condensed ring cyclopentadienyl ligand represented by Formula 1 with a lithium compound and a Group 4 transition metal salt to form a compound represented by the following Formula 5; Transition metal compound containing A manufacturing method is provided:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

(In Formulas 1 to 5, R ¹ to R ¹⁰ are the same as or different from each other, and each independently substituted or unsubstituted with hydrogen, an acetal group or an ether group (C ₁ -C ₂₀ ) Alkyl group, acetal group or ether group substituted or Unsubstituted (C ₂ -C ₂₀ ) Alkenyl group, acetal group or ether group unsubstituted or substituted (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, acetal group or ether group substituted or unsubstituted (C ₆ -C ₂₀ )aryl (C ₁ -C _{20 ) A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an alkyl group, an acetal group, or an ether group ^{; R 1} is ^{connected to R 2} to form a ring R ³ may ^{be connected to R 4} to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring; R ¹¹ to R ¹³ are the same as or different from each other and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ ) Alkyl group, an acetal group or an ether group (C ₂ -C ₂₀ ) alkenyl group, an acetal group or an ether A (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, an acetal group, or an ether group (C ₆ -C ₂₀ )aryl (C ₁ -C ₂₀ )alkyl group unsubstituted or substituted with a group (C 1 -C 20 ) , A (C ₁ -C ₂₀ )silyl group unsubstituted or substituted with an acetal group or an ether group, a (C ₁ -C ₂₀ )alkoxy group unsubstituted or substituted with an acetal group or an ether group, or substituted or unsubstituted with an acetal group or an ether group a cyclic (C ₆ -C ₂₀ )aryloxy group; R ¹¹ and R ¹² , or R ¹² and R ¹³ may be linked to each other to form a ring; M is a Group 4 transition metal; Q ¹ and Q ² are the same as or different from each other, and each independently a halogen group, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, ( C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamido group, (C ₆ -C ₂₀ )arylamido group, or (C ₁ -C ₂₀ )alkylidene group ).

According to another embodiment of the present invention, the transition metal compound represented by Formula 5; and a cocatalyst compound selected from the group consisting of a compound represented by the following formula (6), a compound represented by the following formula (7), and a compound represented by the following formula (8); A method for preparing a metallocene catalyst composition is provided.

[Formula 6]

(In Formula 6, n is an integer of 2 or more; Al is aluminum; O is oxygen; Ra is a halogen group or a (C ₁ -C ₂₀ )hydrocarbyl group unsubstituted or substituted with a halogen group).

[Formula 7]

(In Formula 7, Q is aluminum or boron; Rb is the same as or different from each other, and each independently represents a halogen group or a (C ₁ -C ₂₀ )hydrocarbyl group unsubstituted or substituted with a halogen group).

[Formula 8]

(In Formula 8, [W] ⁺ is a cationic Lewis acid or a cationic Lewis acid to which a hydrogen atom is bonded; Z is a group 13 element; Rc is the same as or different from each other, and each independently a halogen group, (C _1- C _{20 ) A (C 6} -C ₂₀ )aryl group substituted with one or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group; a halogen group, a (C ₁ -C ₂₀ )hydrocarbyl group , substituted with one or two or more substituents selected from the group consisting of an alkoxy group and a phenoxy group (C ₁ -C ₂₀ ) Alkyl group; is).

According to the present invention, a thiophene-condensed ring cyclopentadienyl ligand can be prepared at a relatively high temperature and pressure using chloromethyl alkyl ether, and the prepared ligand can be efficiently separated by using an organic acid. In addition, the thiophene-condensed ring cyclopentadienyl ligand can be prepared in a single reactor by distilling the solvent without step-by-step filtration and purification.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiment of the present invention may be modified in various other forms, and the scope of the present invention is not limited to the embodiments described below.

In the present invention, C _n means that the number of carbon atoms is n.

The method for preparing a thiophene-condensed cyclic cyclopentadienyl ligand according to an embodiment of the present invention comprises: (a) adding a lithium compound and chloromethyl alkyl ether to a tetrahydroquinoline derivative represented by the following formula (2) to obtain the following formula (3) preparing the indicated compound; (b) reacting the compound represented by the formula (3) with the lithium compound, and then adding a compound represented by the following formula (4); and (c) treating the mixture formed in step (b) with an organic acid to isolate the thiophene-condensed cyclic cyclopentadienyl ligand represented by the following formula (1):

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4, R ¹ to R ¹⁰ are the same as or different from each other, and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ ) Alkyl group, acetal group or ether group substituted or Unsubstituted (C ₂ -C ₂₀ ) Alkenyl group, acetal group or ether group unsubstituted or substituted (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, acetal group or ether group substituted or unsubstituted (C ₆ -C ₂₀ )aryl (C ₁ -C _{20 ) A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an alkyl group, an acetal group, or an ether group;

R ¹ may be connected to each other with ^{R 2 to form a ring, R 3} may ^{be connected to R 4} to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring, ;

R ¹¹ to R ¹³ are the same as or different from each other, and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ )alkyl group, an acetal group or an ether group substituted or unsubstituted (C ₂ - C ₂₀₎ alkenyl group, a substituted or unsubstituted group acetal, or ether (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl group, an acetal, or ether group substituted or unsubstituted (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀₎ alkyl group, an acetal, or ether group; substituted or unsubstituted (C ₁ -C ₂₀₎ a silyl group, a substituted or unsubstituted group acetal, or ether (C ₁ -C ₂₀₎ alkoxy group _{, or a (C 6} -C ₂₀ )aryloxy group unsubstituted or substituted with an acetal group or an ether group;

R ¹¹ and R ¹² , or R ¹² and R ¹³ may be linked to each other to form a ring).

Preferably, in Formulas 1 to 4, R ¹ to R ⁵ may each independently be hydrogen or a (C ₁ -C ₂₀ )alkyl group, more preferably R ¹ to R ⁵ are each independently hydrogen or a methyl group. and most preferably R ¹ to R ⁴ are each independently hydrogen or a methyl group, provided ^{that at least one of R 3} and R ⁴ is a methyl group, and R ⁵ may be a methyl group.

Also, preferably, in Formulas 1 to 4, R ⁶ to R ¹³ may each be hydrogen. In this case, accessibility and reactivity of the tetrahydroquinoline derivative starting material can be secured, and it is advantageous for controlling the electronic and steric environment of the transition metal compound represented by Chemical Formula 5 to be described later.

In step (a), when the tetrahydroquinoline derivative represented by Formula 2 is reacted with a lithium compound and then chloromethyl alkyl ether is added, the compound represented by Formula 3 is formed in a temperature range of -30 to 25° C. . Conventionally, when the tetrahydroquinoline derivative represented by Chemical Formula 2 is reacted with a lithium compound and then CO ₂ is added, the reaction proceeds under cryogenic conditions of about -78° C., and it is difficult to set the reaction temperature (Tetrahedron Lett. 1985, 26, 5935; Tetrahedron 1986, 42, 2571; J. Chem. SC. Perkin Trans. 1989, 16.). However, when chloromethyl alkyl ether is used as in the present invention, the reaction proceeds at a relatively high temperature and atmospheric pressure, which is advantageous for setting the reaction temperature.

When the chloromethyl alkyl ether is used, it is not preferable because the yield of the ligand decreases when the reaction temperature is outside the above range.

The chloromethyl alkyl ether may have a C ₁ -C ₁₀ alkyl group, preferably chloromethyl methyl ether.

The lithium compound in step (a) and step (b) is for deprotonation reaction, and may preferably be alkyl lithium. More preferably, n-butyllithium may be used in step (a), and t-butyllithium may be used in step (b).

When a lithium compound is added to the tetrahydroquinoline derivative represented by Formula 2, deprotonation is induced at the nitrogen atom of the tetrahydroquinoline derivative, and then a substitution reaction with chloromethyl alkyl ether proceeds to the compound represented by Formula 3 is formed (step (a)). When a lithium compound is added thereto, an ortho-lithium intermediate is formed, and a mixture comprising a thiophene-condensed ring cyclopentadienyl ligand represented by Formula 1 by reacting with the compound represented by Formula 4 above is formed (step (b)).

Meanwhile, step (c) is a step for separating the thiophene-condensed ring cyclopentadienyl ligand represented by Formula 1 from the mixture formed in step (b), and treating the mixture with an acid to treat the thiophene-condensed ring The cyclopentadienyl ligand can be isolated.

In this case, when a strong acid such as hydrochloric acid is used, the ligand represented by Chemical Formula 1 is precipitated as a salt, and in this process, the unreacted tetrahydroquinoline derivative starting material is precipitated together as a salt and may remain as an impurity. However, when an organic acid is used as in the present invention, the ligand represented by Formula 1 and the unreacted tetrahydroquinoline derivative starting material can be efficiently separated without going through a salt form. The organic acid may be at least one selected from the group consisting of oxalic acid, acetic acid, formic acid and citric acid, preferably oxalic acid.

The present invention provides a thiophene-condensed ring cyclopentadienyl ligand in a single reaction tank (one-pot) by removing the solvent used in step (a), step (b) and step (c) by distillation without a special purification process. can be manufactured. Examples of the solvent include hydrocarbon-based solvents such as pentane, hexane, heptana, nonane, decane, cyclopentane, and cyclohexane, ether-based solvents such as diethyl ether and tetrahydrofuran, and acetate-based solvents such as methyl acetate and ethyl acetate, It is not particularly limited as long as it is removed by distillation without a purification process.

The method for producing a transition metal compound according to another embodiment of the present invention comprises (a) adding a lithium compound and chloromethyl alkyl ether to the tetrahydroquinoline derivative represented by Formula 2 to prepare a compound represented by Formula 3 step; (b) reacting the compound represented by Formula 3 with the lithium compound, and then adding the compound represented by Formula 4; (c) treating the organic acid to separate the thiophene-condensed ring cyclopentadienyl ligand represented by Formula 1; and (d) treating the thiophene-condensed cyclic cyclopentadienyl ligand represented by Formula 1 with a lithium compound and a Group 4 transition metal salt to form a compound represented by Formula 5 below:

[Formula 5]

In Formula 5, R ¹ to R ¹³ are as defined in Formulas 1 to 4.

In Formula 5, M is a Group 4 transition metal, Q ¹ and Q ² are the same as or different from each other, and each independently a halogen group, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C ₆ -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl (C ₁ - C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkylamido group, (C ₆ -C ₂₀ )arylamido group, or (C ₁ -C ₂₀ )alkylidene group.

In the transition metal compound represented by Formula 5, the Group 4 transition metal M may include titanium, zirconium, hafnium, and the like. In addition, Q ¹ and Q ² are each independently a methyl group or chlorine, R ¹ to R ⁵ are each independently hydrogen or a methyl group, preferably R ¹ to R ⁴ are each independently hydrogen or a methyl group, provided that R ³ and ^{at least one of R 4} is a methyl group, R ⁵ is a methyl group, and R ⁶ to R ¹³ are each hydrogen is preferred for electronic and steric environmental control around the metal.

Steps (a), (b), and (c) proceed in the same manner as the reaction for forming the thiophene-condensed ring cyclopentadienyl ligand.

In step (d), by adding 2 molar equivalents of a lithium compound to the ligand represented by Formula 1 formed in step (c) to induce a deprotonation reaction, a dilithium compound of a cyclopentadienyl anion and an amide anion was prepared. After that, (Q ¹ )(Q ² )MCl ₂ is added thereto to remove 2 molar equivalents of LiCl.

In another method, by reacting the compound represented by Formula 2 with the compound M(NMe ₂ ) ₄ to remove 2 molar equivalents of HNMe ₂ ^{, Q 1} and Q ² are NMe ₂ at the same time to obtain a transition metal compound represented by Formula 5 and Me ₃ SiCl or Me ₂ SiCl ₂ reacted thereto to change the NMe ₂ ligand to a chlorine ligand.

When Q ¹ and Q ² are halogen, the method may ^{further comprise alkylating Q 1} and Q ² using an alkylation reagent, wherein the alkylation reagent is an alkyllithium having an _{(C 1} -C _{10 )alkyl group or} An alkyl magnesium halide may be used, but is not limited thereto.

The transition metal compound represented by Chemical Formula 5 is used as a catalyst for olefin polymerization, and exhibits higher activity than when a catalyst having no thiophene-condensed ring is used. Therefore, it is possible to prepare a polymer having a higher molecular weight without significantly impairing the alpha-olefin copolymerizability.

A method for preparing a metallocene catalyst composition according to another embodiment of the present invention comprises: a transition metal compound represented by Chemical Formula 5; and reacting one or two or more cocatalyst compounds selected from the group consisting of a compound including a unit represented by the following formula (6), a compound represented by the following formula (7), and a compound represented by the following formula (8).

[Formula 6]

In Formula 6, n is an integer of 2 or more;

Al is aluminum;

O is oxygen;

Ra is a halogen group or a (C ₁ -C ₂₀ )hydrocarbyl group substituted or unsubstituted with a halogen group;

[Formula 7]

In Formula 7, Q is aluminum or boron;

Rb is the same as or different from each other, and each independently represents a halogen group or a (C ₁ -C ₂₀ )hydrocarbyl group substituted or unsubstituted with a halogen group;

[Formula 8]

In Formula 8, [W] ⁺ is a cationic Lewis acid or a cationic Lewis acid to which a hydrogen atom is bonded;

Z is a group 13 element;

Rc is the same as or different from each other, and each independently substituted with one or two or more substituents selected from the group consisting _{of a halogen group, (C 1} -C _{20 )hydrocarbyl group, an alkoxy group and a phenoxy group (C 6} -C ₂₀ ) aryl group; A halogen group, (C ₁ -C _{20 ) A (C 1} -C ₂₀ ) alkyl group substituted with one or two or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group;

The cocatalyst compound is included in the catalyst composition together with the transition metal compound represented by Formula 5 to activate the transition metal compound. Specifically, in order for the transition metal compound to become an active catalyst component used for olefin polymerization, the ligand (Q ₁ Q ₂ ) in the transition metal compound is extracted to cationize the central metal (M) and a counterion having a weak binding force, That is, the compound including the unit represented by Formula 6, which can act as an anion, the compound represented by Formula 7, and the compound represented by Formula 8 act together as a cocatalyst.

The 'unit' represented by Formula 6 is a structure in which n structures in [ ] are connected in the compound, and if the unit represented by Formula 6 is included, other structures in the compound are not particularly limited, and the repeating unit of Formula 6 may be a cluster type, such as a spherical compound, linked to each other.

The compound including the unit represented by the formula (6) is not particularly limited, and is preferably an alkylaluminoxane. Non-limiting examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like. Considering the activity of the transition metal compound, methylaluminoxane may be preferably used.

In addition, the compound represented by Formula 7 is not particularly limited as an alkyl metal compound, and non-limiting examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, and triiso. Propyl aluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like. Considering the activity of the transition metal compound, one or two or more selected from the group consisting of trimethylaluminum, triethylaluminum and triisobutylaluminum may be preferably used.

When considering the activity of the transition metal compound, the compound represented by Formula 8 is a ^{dimethylanilinium cation when [W] +} is a cationic Lewis acid to which a hydrogen atom is bonded, and [W] ⁺ is a cationic Lewis acid, [ (C ₆ H ₅ ) ₃ C] ⁺ , and [Z(Rc) ₄ ] ^- is [B(C ₆ F ₅ ) ₄ ] ^- , and may be preferably used.

The compound represented by the formula (8) is not particularly limited, but ^{non-limiting examples of the case where [W] +} is a cationic Lewis acid to which a hydrogen atom is bonded include triethylammonium tetrakisphenylborate, tributylammoniumtetrakisphenylborate, trimethyl Ammonium tetrakisphenylborate, tripropylammonium tetrakisphenylborate, trimethylammonium tetrakis(p-tolyl)borate, tripropylammonium tetrakis(p-tolyl)borate, trimethylammonium tetrakis(o,p -Dimethylphenyl)borate, triethylammonium tetrakis(o,p-dimethylphenyl)borate, tributylammonium tetrakis(p-trifluoromethylphenyl)borate, trimethylammonium tetrakis(p-trifluoromethylphenyl) ) borate, tributylammonium tetrakispentafluorophenylborate, anilinium tetrakisphenylborate, anilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluoro Phenyl) borate, N,N-diethylaniliniumtetrakispetylborate, N,N-diethylaniliniumtetrakisphenylborate, N,N-diethylaniliniumtetrakispentafluorophenylborate, di Ethylammonium tetrakispentafluorophenyl borate, triphenylphosphonium tetrakisphenyl borate, trimethylphosphonium tetrakisphenyl borate, triphenylcarbonium tetrakis (p-trifluoromethylphenyl) borate, triphenylcarbonium tetrakispentafluorophenylborate, dimethylaniliniumtetrakis(pentafluorophenyl)borate, and the like, ^{non-limiting examples where [W] +} is a cationic Lewis acid, triphenylcarboniumtetrakisphenylborate, Triphenylcarboniumtetrakis(p-tolyl)borate, triphenylcarboniumtetrakis(o,p-dimethylphenyl)borate, triphenylcarboniumtetrakis(p-trifluoromethylphenyl)borate, triphenyl Carbonium tetrakispentafluorophenyl borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate, and the like.

Example

Hereinafter, embodiments of the present invention will be described in detail. The following examples are only for the understanding of the present invention, but do not limit the present invention.

<Example>

[Ligand Preparation Step]

A Schlenk flask containing a solution of 1,2,3,4-tetrahydroquinaldine (59.7 g, 405 mmol) and n-hexane (800 mL) was immersed in a low temperature bath at 0 ° C to lower the temperature, and then, under stirring, n-butyllithium (178.3 mL, 446 mmol, 2.5 M hexane solution) was slowly injected under a nitrogen atmosphere. After stirring at 0 °C for about an hour, the temperature was slowly raised to room temperature. A white solid was precipitated, and the generated butane gas was removed through a bubbler, and then the reaction was carried out at room temperature overnight. The solvent was removed using a vacuum pump without further purification. Diethyl ether (600 mL) was injected into the flask, the temperature was lowered to 0 °C, and chloromethyl methyl ether was injected.

After stirring at 0 °C for one hour, the temperature was slowly raised to room temperature, and the mixture was stirred at room temperature again overnight. At -30 °C, tetrahydrofuran (32.1 g, 446 mmol) and t-butyllithium (262 mL, 446 mmol, 1.7 M pentane solution) were sequentially injected under a nitrogen atmosphere, followed by stirring for two hours. Then, a diethyl ether solution (600 mL) in which the compound represented by Formula 4 (R ¹ , R ² , R ⁴ : Me, R ³ : H; 62.1 g, 345 mmol) was dissolved was injected under a nitrogen atmosphere. After stirring at -30 °C for one hour, the temperature was slowly raised to room temperature, and the mixture was stirred at room temperature overnight.

At 0 °C, 2 M HCl (750 mL) was injected into the reaction flask, and the reaction was terminated by stirring at room temperature for 30 minutes. The solution was transferred to a separatory funnel and the organic layer was extracted. The extracted organic layer was washed once more with 1 M oxalic acid solution to completely remove the tetrahydroquinaldine starting material. After removing the solvent and re-dissolving in n-hexane, a 6 M HCl (321 mL) solution is added to form a salt. The resulting salt was washed with n-hexane, dissolved in ethyl acetate, and neutralized with a _{Na 2} CO _{3 solution.} The organic layer was extracted and _{dried using MgSO 4} to obtain a ligand (62.7 g, 50%).

[Metal complexation step]

Put 53.4 g of the synthesized ligand in a Schlenk flask containing hexane (600 mL) and lower the temperature to 0 °C. n-Butyllithium (151.8 mL, 2.5 M hexane solution) was slowly injected under a nitrogen atmosphere, and the mixture was raised to room temperature and stirred overnight. The hexane in the flask was removed by filtration under nitrogen atmosphere, and diethyl ether (600 mL) was added. The temperature is lowered to -50 ℃, and TiCl ₄ /diethyl ether adduct (TiCl ₄ 172 mmol) is slowly added to the reaction flask. After stirring for two hours, raise to room temperature and stir overnight. The solvent in the flask is distilled off, and the metal complexed catalyst is extracted with hexane and collected in another Schlenk flask. Hexane was distilled off in the flask to obtain a metal complexed catalyst (69.2 g, 94%).

[Methylation step]

Pour diethyl ether (900 mL) into the flask containing the metal complexed catalyst. Lower the temperature of the reaction flask to -50 °C, and slowly inject methylmagnesium bromide (119 mL, 3.0 M diethyl ether solution). After stirring for 3 hours, the temperature was raised to room temperature and stirred overnight. Diethyl ether is distilled off in the flask, and the methylated catalyst is extracted with hexane and collected in another Schlenk flask. The methylated catalyst was obtained by distilling off hexane (50 g, 80%).

<Comparative example>

[Ligand Preparation Step]

A Schlenk flask containing a solution of 1,2,3,4-tetrahydroquinaldine (20 g, 136 mmol) and n-hexane (280 mL) was immersed in a low-temperature bath at 0 ° C to lower the temperature, and then, under stirring, n-butyllithium (54.3 mL, 136 mmol, 2.5 M hexane solution) was slowly injected under a nitrogen atmosphere. After stirring at 0 °C for about an hour, the temperature was slowly raised to room temperature. A white solid was precipitated, and the generated butane gas was removed through a bubbler, and then the reaction was carried out at room temperature overnight. The resulting solid was filtered under nitrogen atmosphere and washed with n-hexane (21 g). Diethyl ether (200 mL) was injected into the Schlenk flask containing the purified white solid, the temperature was lowered to -78 °C, and carbon dioxide was injected. As soon as carbon dioxide was injected, the solution in the slurry state became a transparent homogeneous solution.

After stirring at -78 °C for one hour, the excess carbon dioxide was removed through a bubbler while slowly raising the temperature to room temperature. A white solid precipitated again. The reaction was carried out at room temperature overnight. At -50 °C, tetrahydrofuran (9.80 g, 136 mmol) and t-butyllithium (80 mL, 136 mmol, 1.7 M pentane solution) were sequentially injected under a nitrogen atmosphere and stirred for two hours. Then, a diethyl ether solution (200 mL) in which the compound represented by Formula 4 (R ¹ , R ² , R ⁴ : Me, R ³ : H; 22.4 g, 115 mmol) was dissolved was injected under a nitrogen atmosphere. After stirring at -50 °C for one hour, the temperature was slowly raised to room temperature, and then stirred at room temperature overnight.

At 0 °C, 2M HCl (250 mL) was injected into the reaction flask, and the reaction was terminated by stirring at room temperature for 30 minutes. The solution was transferred to a separatory funnel and the organic layer was extracted. After removing the solvent and re-dissolving in n-hexane, a 6M HCl (108 mL) solution is added to form a salt. The resulting salt was washed with n-hexane, dissolved in ethyl acetate, and neutralized with a _{Na 2} CO _{3 solution.} The organic layer was extracted and _{dried using MgSO 4} to obtain a ligand (41.6 g, 52%).

[Metal complexation step and methylation step]

The metal complexation and methylation reaction were carried out in the same manner and in the same manner as described in the above Examples to obtain a methylated catalyst (21 g, 78%).

<Polyethylene Polymerization>

After replacing the inside of the high pressure reactor (internal capacity: 2.8 L, stainless steel) with nitrogen at room temperature, 1 L of n-hexane and 2.0 mmol of triisobutylaluminum were added. Then, 250.0 mL of 1-octene, a comonomer, was injected. Then, 135.0 g of ethylene gas was injected, and the temperature of the reactor was preheated to 140 °C. Then, in a mixed solution of the main catalyst compound (7.5 μmol) and triisobutyl aluminum (187.5 μmol) formed from the ligands of Examples and Comparative Examples, dimethylanilinium tetrakis(pentablue orophenyl)borate cocatalyst compound (45.0 μmol) was mixed and injected into the reactor to carry out a polymerization reaction for 5 minutes to prepare polyethylene.

catalytic activity
(kg/mmol _Ti hr) Mw
(g/mol) MWD 1-octene content
(wt%) Tm
(℃) Example 78.40 254900 1.92 40.4 66 comparative example 92.64 252900 2.85 39.4 65

As can be seen in Table 1, the metallocene catalysts formed from the ligands prepared in Examples and Comparative Examples show similar levels of catalytic activity, and it can be confirmed that polyethylene prepared in the presence of the catalyst also has similar physical properties. have. Therefore, the preparation of the thiophene-condensed ring cyclopentadienyl ligand described in the present invention in one-pot is an effective method for preparing a metallocene catalyst for preparing a polyolefin copolymer.

Claims (11)

(a) adding a lithium compound and chloromethyl alkyl ether to a tetrahydroquinoline derivative represented by the following formula (2) to form a compound represented by the following formula (3);
(b) reacting the compound represented by the formula (3) with the lithium compound, and then adding a compound represented by the following formula (4); and
(c) treating the mixture formed in step (b) with an organic acid to separate the thiophene-condensed cyclic cyclopentadienyl ligand represented by the following formula (1);
A thiophene-condensed ring cyclopentadienyl ligand preparation method comprising:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 1 to 4, R ¹ to R ¹⁰ are the same as or different from each other, and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ ) Alkyl group, acetal group or ether group substituted or Unsubstituted (C ₂ -C ₂₀ ) Alkenyl group, acetal group or ether group unsubstituted or substituted (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, acetal group or ether group substituted or unsubstituted (C ₆ -C ₂₀ )aryl (C ₁ -C _{20 ) A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an alkyl group, an acetal group, or an ether group;
R ¹ may ^{be connected to R 2} to form a ring, R ³ may ^{be connected to R 4} to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring, ;
R ¹¹ to R ¹³ are the same as or different from each other, and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ )alkyl group, an acetal group or an ether group substituted or unsubstituted (C ₂ - C ₂₀ ) Unsubstituted or substituted with an alkenyl group, an acetal group, or an ether group (C ₁ -C ₂₀ ) Alkyl (C ₆ -C ₂₀ )aryl group, an acetal group or an ether group (C ₆ -C _{20 )} ) aryl (C ₁ -C ₂₀₎ alkyl group, an acetal, or ether group; substituted or unsubstituted (C ₁ -C ₂₀₎ a silyl group, a substituted or unsubstituted group acetal, or ether (C ₁ -C ₂₀₎ alkoxy group _{, or a (C 6} -C ₂₀ )aryloxy group unsubstituted or substituted with an acetal group or an ether group;
R ¹¹ and R ¹² , or R ¹² and R ¹³ may be linked to each other to form a ring).
According to claim 1,
R ¹ to R ⁴ are each independently hydrogen or a methyl group, provided that at least one of ^{R 3} and R ^{4 is a methyl group;}
R ⁵ is a methyl group;
R ⁶ to R ¹³ are each hydrogen. A method for preparing a thiophene-fused ring cyclopentadienyl ligand.
According to claim 1,
The chloromethyl alkyl ether is _{a thiophene having a C 1} -C ₁₀ alkyl group-condensed ring cyclopentadienyl ligand preparation method.
According to claim 1,
The reaction temperature of step (a) is -30 to 25 ℃ thiophene-condensed ring cyclopentadienyl ligand preparation method.
According to claim 1,
The organic acid is at least one selected from the group consisting of oxalic acid, acetic acid, formic acid and citric acid.
According to claim 1,
The lithium compound is alkyl lithium thiophene-condensed ring cyclopentadienyl ligand manufacturing method.
(a) preparing a compound represented by the following formula (3) by adding a lithium compound and chloromethyl alkyl ether to the tetrahydroquinoline derivative represented by the following formula (2);
(b) reacting the compound represented by the formula (3) with the lithium compound, and then adding a compound represented by the following formula (4);
(c) treating the mixture formed in step (b) with an organic acid to separate the thiophene-condensed cyclic cyclopentadienyl ligand represented by the following formula (1); and
(d) treating the thiophene-condensed ring cyclopentadienyl ligand represented by Formula 1 with a lithium compound and a Group 4 transition metal salt to form a compound represented by Formula 5;
A method for preparing a transition metal compound comprising:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

(In Formulas 1 to 5, R ¹ to R ¹⁰ are the same as or different from each other, and each independently substituted or unsubstituted with hydrogen, an acetal group or an ether group (C ₁ -C ₂₀ ) Alkyl group, acetal group or ether group substituted or Unsubstituted (C ₂ -C ₂₀ ) Alkenyl group, acetal group or ether group unsubstituted or substituted (C ₁ -C ₂₀ )alkyl (C ₆ -C ₂₀ )aryl group, acetal group or ether group substituted or unsubstituted (C ₆ -C ₂₀ )aryl (C ₁ -C _{20 ) A (C 1} -C ₂₀ )silyl group unsubstituted or substituted with an alkyl group, an acetal group, or an ether group;
R ¹ may be connected to each other with ^{R 2 to form a ring, R 3} may ^{be connected to R 4} to form a ring, and ^{two or more of R 5} to R ¹⁰ may be connected to each other to form a ring, ;
R ¹¹ to R ¹³ are the same as or different from each other, and each independently hydrogen, an acetal group or an ether group substituted or unsubstituted (C ₁ -C ₂₀ )alkyl group, an acetal group or an ether group substituted or unsubstituted (C ₂ - C ₂₀₎ alkenyl group, a substituted or unsubstituted group acetal, or ether (C ₁ -C ₂₀₎ alkyl (C ₆ -C ₂₀₎ aryl group, an acetal, or ether group substituted or unsubstituted (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀₎ alkyl group, an acetal, or ether group; substituted or unsubstituted (C ₁ -C ₂₀₎ a silyl group, a substituted or unsubstituted group acetal, or ether (C ₁ -C ₂₀₎ alkoxy group _{, or a (C 6} -C ₂₀ )aryloxy group unsubstituted or substituted with an acetal group or an ether group;
R ¹¹ and R ¹² , or R ¹² and R ¹³ may be linked to each other to form a ring;
M is a Group 4 transition metal;
Q ¹ and Q ² are the same as or different from each other, and each independently a halogen group, (C ₁ -C ₂₀ )alkyl group, (C ₂ -C ₂₀ )alkenyl group, (C ₂ -C ₂₀ )alkynyl group, (C _{6 )} -C ₂₀ )aryl group, (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl group, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl group, (C ₁ -C ₂₀ )alkyl an amido group, a (C ₆ -C ₂₀ )arylamido group, or a (C ₁ -C ₂₀ )alkylidene group).
8. The method of claim 7,
R ¹ to R ⁴ are each independently hydrogen or a methyl group, provided that at least one of ^{R 3} and R ^{4 is a methyl group;}
R ⁵ is a methyl group;
R ⁶ to R ¹³ are each hydrogen;
M is titanium or zirconium;
Q ¹ and Q ² are each independently a methyl group or chlorine (Cl), a method for preparing a transition metal compound
8. The method of claim 7,
In Chemical Formula 5, when Q ¹ and Q ² are halogen, a method for preparing a transition metal compound further comprising alkylating ^{Q 1} and Q ^{2 using an alkylation reagent.}
10. The method of claim 9,
The alkylation reagent is (C ₁ -C ₁₀ ) A method for producing a transition metal compound, wherein the alkyl lithium or alkyl magnesium halide having an alkyl group.
A transition metal compound represented by Formula 5, prepared according to any one of claims 7 to 10; and
A compound comprising a unit represented by the following formula (6), a compound represented by the following formula (7), and one or two or more cocatalyst compounds selected from the group consisting of a compound represented by the following formula (8); metal comprising the step of reacting Method for preparing the Rosen catalyst composition:

[Formula 6]

(In Formula 6, n is an integer of 2 or more; Al is aluminum; O is oxygen; Ra is a halogen group or a (C ₁ -C ₂₀ )hydrocarbyl group unsubstituted or substituted with a halogen group).
[Formula 7]

(In Formula 7, Q is aluminum or boron; Rb is the same as or different from each other, and each independently represents a halogen group or a (C ₁ -C ₂₀ )hydrocarbyl group unsubstituted or substituted with a halogen group).
[Formula 8]

(In Formula 8, [W] ⁺ is a cationic Lewis acid or a cationic Lewis acid to which a hydrogen atom is bonded; Z is a group 13 element; Rc is the same as or different from each other, and each independently a halogen group, (C _1- C _{20 ) A (C 6} -C ₂₀ )aryl group substituted with one or more substituents selected from the group consisting of a hydrocarbyl group, an alkoxy group and a phenoxy group; a halogen group, a (C ₁ -C ₂₀ )hydrocarbyl group , substituted with one or two or more substituents selected from the group consisting of an alkoxy group and a phenoxy group (C ₁ -C ₂₀ ) Alkyl group; is).