KR102054466B1 - Catalystic composition comprising transition metal compound, and for preparing polymers using the same - Google Patents

Abstract

The present invention relates to a catalyst composition comprising a transition metal compound and a dialkylzinc compound, and a method for preparing a polymer using the same, wherein the catalyst composition according to the present invention is formed around a metal site by an amido group connected in a ring form to a phenylene bridge. Since it is very stable with a solid pentagonal ring structure and thus structurally easy access of monomers, and includes a transition metal compound having a fused structure of thiophene fused benzene ring, and a dialkyl zinc compound, By using this, it is possible to prepare a polymer having a narrow MWD, excellent copolymerizability and high molecular weight even in a low density region.

Description

Catalyst composition comprising a transition metal compound and a method for producing a polymer using the same {CATALYSTIC COMPOSITION COMPRISING TRANSITION METAL COMPOUND, AND FOR PREPARING POLYMERS USING THE SAME}

The present invention relates to a catalyst composition comprising a transition metal compound and a method for producing a polymer using the same, and more particularly to a catalyst composition capable of producing a polymer having a narrow molecular weight distribution, including a transition metal compound and a dialkyl zinc compound. It relates to a method for producing a polymer using the same.

Dow Company in the early 1990s [Me ₂ Si (Me ₄ C ₅ ) N t Bu] TiCl ₂ (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) (US Pat. No. 5,064,802). In the copolymerization reaction of ethylene and alpha-olefin, the CGC is superior to the metallocene catalysts known to the prior art. It can be summarized in two ways: (1) to produce high molecular weight polymers with high activity even at high polymerization temperatures, and (2) to high sterically hindered alpha-olefins such as 1-hexene and 1-octene. The copolymerizability is also very good. In addition, during the polymerization reaction, various characteristics of CGC are gradually known, and efforts to synthesize derivatives thereof and use them as polymerization catalysts have been actively conducted in academia and industry.

One approach has been to synthesize and polymerize metal compounds in which various other bridges and nitrogen substituents have been introduced instead of silicon bridges. Representative metal compounds known to date are listed as compounds (1) to (4) (Chem. Rev. 2003, 103, 283).

Compounds (1) to (4) have phosphorus (1), ethylene or propylene (2), methylidene (3), and methylene (4) bridges instead of CGC-structured silicon bridges, respectively, but ethylene polymerization Alternatively, when the copolymerization with the alpha-olefin is applied, there are no improved results in terms of activity or copolymerization performance compared to CGC.

In another approach, many compounds composed of oxido ligands instead of the amido ligands of CGC have been synthesized, and some polymerization has been attempted using the compounds. The examples are as follows.

Compound (5) was reported by T. J. Marks et al. Characterized in that the Cp (cyclopentadiene) derivative and the oxido ligand were crosslinked by an ortho-phenylene group (Organometallics 1997, 16, 5958). Compounds with the same crosslinks and polymerizations using them have also been reported by Mu et al. (Organometallics 2004, 23, 540). In addition, it was reported by Rothwell et al. That an indenyl ligand and an oxido ligand were crosslinked by the same ortho-phenylene group (Chem. Commun. 2003, 1034). Compound (6), reported by Whitby et al., Is characterized by the piercing of cyclopentanienyl and oxidant ligands by three carbons (Organometallics 1999, 18, 348). These catalysts are syndiotactic. ) Have been reported to be active in polystyrene polymerization. Similar compounds have also been reported by Hessen et al. (Organometallics 1998, 17, 1652). Compound (7), reported by Rau et al., Is characterized by its activity in ethylene polymerization and ethylene / 1-hexene copolymerization at high temperatures and pressures (210 ° C, 150 MPa) (J. Organomet. Chem. 2000, 608, 71). . In addition, a patent synthesis (8) and a high temperature, high pressure polymerization using the same structure has been patented by Sumitomo, Inc. (US Pat. No. 6,548,686). However, few of the above attempts have actually been applied to commercial plants. Therefore, there is a need for catalysts that exhibit improved polymerization performance, and a method for simple production of such catalysts.

U.S. Patent Registration 5,064,802 U.S. Patent No. 6,548,686

Chem. Rev. 2003, 103, 283 Organometallics 1997, 16, 5958 Organometallics 2004, 23, 540 Chem. Commun. 2003, 1034 Organometallics 1999, 18, 348 Organometallics 1998, 17, 1652 J. Organomet. Chem. 2000, 608, 71

The problem to be solved of the present invention is to provide a catalyst composition comprising a transition metal compound and a dialkyl zinc compound.

Another object of the present invention is to provide a method for producing a polymer using the catalyst composition.

In order to solve the above problems, the present invention

A catalyst composition comprising a transition metal compound of Formula 1 and a dialkylzinc compound of Formula 2 is provided:

In Chemical Formula 1,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms,

R ₁ to R ₆ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms,

R ₇ to R ₉ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two of R ₇ to R _{9 may} be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

Cy is a 5 or 6 membered aliphatic ring,

R, R ₁₆ and R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, an integer of 0 to 4 when Cy is a 6-membered aliphatic ring,

In Chemical Formula 2,

R ₁₈ and R _{19 's} are each independently alkyl having 1 to 20 carbon atoms.

In order to solve the above other problem, the present invention

It provides a method for producing a polymer using the catalyst composition.

The catalyst composition according to the present invention is very stably maintained in a five-membered ring structure around the metal site by the amido group linked in a ring form to the phenylene bridge, thereby structurally easily accessing the monomers, and the benzene ring is fused. It includes a transition metal compound having a structure in which the thiophene structure is fused, and a dialkyl zinc compound, so that it is possible to prepare a polymer having a narrow molecular weight distribution (MWD), excellent copolymerizability and high molecular weight even in a low density region. Do.

The catalyst composition according to the present invention includes a transition metal compound of Formula 1 and a dialkylzinc compound of Formula 2 below.

[Formula 1]

[Formula 2]

In Chemical Formula 1,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms,

R ₁ to R ₆ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms,

R ₇ to R ₉ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two of R ₇ to R _{9 may} be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

Cy is a 5 or 6 membered aliphatic ring,

R, R ₁₆ and R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, an integer of 0 to 4 when Cy is a 6-membered aliphatic ring,

m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, an integer of 0 to 4 when Cy is a 6-membered aliphatic ring,

In Chemical Formula 2,

R ₁₈ and R _{19 's} are each independently alkyl having 1 to 20 carbon atoms.

The transition metal compound represented by Chemical Formula 1 has a metal site connected by a cyclopentadienyl ligand in which an amido group is linked to a phenylene bridge in a ring form, so that the Cp-MN angle is structurally narrow, and a monomer is approached. The Q1-M-Q2 angle is characterized by keeping it wide. In addition, unlike the CGC structure linked by the silicon bridge, in the compound structure represented by Formula 1, cyclopentadiene, phenylene bridge, nitrogen, and metal sites, in which benzothiophene is fused by a ring-shaped bond, are connected in sequence. It is more stable and has a solid ring structure. Therefore, when these compounds are reacted with methylaluminoxane or a cocatalyst such as B (C ₆ F ₅ ) ₃ to be activated and then applied to olefin polymerization, they exhibit characteristics such as high activity, high molecular weight and high copolymerization even at high polymerization temperatures. It is possible to produce polyolefins having. Particularly, due to the structural characteristics of the catalyst, not only linear low density polyethylene having a density of 0.910 to 0.930 g / cc, but also a large amount of alpha-olefins can be introduced, thereby making it possible to prepare an ultra low density polyolefin copolymer having a density of less than 0.910 g / cc. . In particular, the catalyst composition of the present invention comprising the transition metal compound has a narrower molecular weight distribution (weight average molecular weight / number average molecular weight) (NWD) compared to CGC, excellent copolymerizability, and can produce a polymer having a high molecular weight even in a low density region. have. In addition, various substituents may be introduced into the benzothiophene-fused cyclopentadienyl and quinoline-based compounds, which may ultimately control the structure and physical properties of the polyolefin produced by easily controlling the electronic and three-dimensional environment around the metal. .

According to one embodiment of the present invention, the compound of Formula 1 may be a compound of Formula 3 or 4.

In Chemical Formula 3, R ₁₂ to R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

The remaining substituents are as defined in Formula 1 above.

In Chemical Formula 4,

R ₂₀ to R ₂₃ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

The remaining substituents are as defined in Formula 1 above.

According to an example of the present invention, R ₁ and R ₂ may be alkyl having 1 to 20 carbon atoms.

According to another example of the present invention, R ₁ and R ₂ may be alkyl having 1 to 6 carbon atoms.

According to another example of the present invention, R ₁ and R ₂ may be methyl.

According to an example of the present invention, R ₃ to R ₆ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Or alkenyl having 2 to 20 carbon atoms.

According to another embodiment of the present invention, each of R ₃ to R ₆ is independently hydrogen; Or alkyl having 1 to 20 carbon atoms.

According to another example of the present invention, R ₃ to R ₆ may be hydrogen.

According to an embodiment of the present invention, R ₁₂ to R ₁₇ in Chemical Formula 3 are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Or alkenyl having 2 to 20 carbon atoms.

According to another embodiment of the present invention, R ₁₂ to R ₁₇ in Chemical Formula 3 are each independently hydrogen; Or alkyl having 1 to 20 carbon atoms.

According to another example of the present invention, R ₁₂ to R ₁₇ in Formula 3 may be hydrogen.

According to one embodiment of the present invention, R ₁₂ to R ₁₆ in Chemical Formula 3 may be hydrogen, and R ₁₇ may be alkyl having 1 to 20 carbon atoms.

According to another example of the present invention, R ₁₂ to R ₁₆ in Chemical Formula 3 may be hydrogen, and R ₁₇ may be methyl.

According to one embodiment of the present invention, R ₂₀ to R ₂₃ in Formula 4 may each independently be hydrogen; Alkyl having 1 to 20 carbon atoms; Or alkenyl having 2 to 20 carbon atoms.

According to another embodiment of the present invention, R ₂₀ to R ₂₃ in Formula 4 are each independently hydrogen; Or alkyl having 1 to 20 carbon atoms.

According to another example of the present invention, R ₂₀ to R ₂₃ in Formula 4 may be hydrogen.

According to one embodiment of the present invention, R ₂₀ to R ₂₂ in Chemical Formula 3 may be hydrogen, and R ₂₃ may be alkyl having 1 to 20 carbon atoms.

According to another embodiment of the present invention, R ₂₀ to R ₂₂ in Formula 4 may be hydrogen, R ₂₃ may be methyl.

According to an example of the invention, M may be Ti, Hf or Zr.

The transition metal compound represented by Chemical Formula 1 may be a compound represented by any one of the following Chemical Formulas, but is not limited thereto.

(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

Each substituent defined in the present specification will be described in detail as follows.

As used herein, the term "halogen" means fluorine, chlorine, bromine or iodine, unless stated otherwise.

As used herein, the term 'alkyl' refers to a straight or branched chain hydrocarbon residue unless otherwise indicated.

As used herein, the term 'alkenyl' refers to a straight or branched alkenyl group unless otherwise indicated.

The branched chain is alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms.

According to one embodiment of the present invention, the silyl group is trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triisopropylsilyl, triisobutylsilyl, triethoxysilyl, triphenylsilyl, tris ( Trimethylsilyl) silyl and the like, but are not limited to these examples.

According to an example of the present invention, the aryl group preferably has 6 to 20 carbon atoms, and specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto.

The alkylaryl group means an aryl group substituted by the alkyl group.

The arylalkyl group means an alkyl group substituted by the aryl group.

The ring (or heterocyclic group) means a monovalent aliphatic or aromatic hydrocarbon group having 5 to 20 carbon atoms and containing one or more hetero atoms, and may be a single ring or a condensed ring of two or more rings. In addition, the heterocyclic group may be substituted or unsubstituted with an alkyl group. Examples thereof include indolin, tetrahydroquinoline, and the like, but the present invention is not limited thereto.

The alkyl amino group means an amino group substituted by the alkyl group, and there are a dimethylamino group, a diethylamino group, and the like, but is not limited thereto.

According to one embodiment of the present invention, the aryl group preferably has 6 to 20 carbon atoms, specifically, phenyl, naphthyl, anthracenyl, pyridyl, dimethylanilinyl, anisolyl, and the like, but is not limited thereto. no.

The compound of Formula 1 may be prepared by a method comprising the following steps a) to d):

a) preparing a compound represented by the following Chemical Formula 6 by reacting the amine compound represented by the following Chemical Formula 5 with alkyllithium, and then adding a compound including a protecting group (-R ₀ );

b) reacting the compound represented by Chemical Formula 6 with alkyllithium, and then adding a ketone compound represented by Chemical Formula 7 to prepare an amine compound represented by Chemical Formula 8;

c) reacting the compound represented by Formula 8 with n-butyllithium to prepare a dilithium compound represented by Formula 9 below; And

d) preparing a transition metal compound represented by Chemical Formula 1 by reacting the compound represented by Chemical Formula 9 with MCl ₄ (M = group 4 transition metal) and an organolithium compound.

In Chemical Formulas 5 to 9,

R 'is hydrogen,

R ₀ is a protecting group,

Other substituents are as defined in the formula (1).

The compound including a protecting group in step a) may be selected from trimethylsilyl chloride, benzyl chloride, t-butoxycarbonyl chloride, benzyloxycarbonyl chloride and carbon dioxide.

When the compound including the protecting group is carbon dioxide, Chemical Formula 6 may be a lithium carbamate compound represented by Chemical Formula 6a.

 [Formula 6a]

Each substituent in Formula 6a is as defined in Formula 5.

According to a specific example, the compound of Chemical Formula 1 may be prepared by the following Scheme 1.

Scheme 1

In Scheme 1, each substituent is as defined in the formula (1), n is 0 or 1.

R ₁₈ and in the dialkylzinc compound of Formula 2 included in the catalyst composition R ₁₉ may be each independently alkyl having 1 to 20 carbon atoms, and R ₁₈ and R ₁₉ may be each independently alkyl having 1 to 8 carbon atoms.

Specifically, the dialkyl zinc compound of Formula 2 may be at least one selected from the group consisting of diethyl zinc, dipropyl zinc, dibutyl zinc and ethyl propyl zinc, more specifically the dialkyl zinc compound of Formula 2 Diethylzinc.

The dialkyl zinc compound of Chemical Formula 2 may be mixed in an amount of 1 to 200 equivalents based on 1 equivalent of the transition metal compound of Chemical Formula 1, and specifically, about 10 to about 100 equivalents of 1 equivalent of the transition metal compound of Chemical Formula 1 It can be mixed in an amount of.

The catalyst composition may further comprise a promoter. As the promoter, those known in the art may be used.

For example, the catalyst composition may further include at least one of the following Chemical Formulas 10 to 12 as a cocatalyst.

[Formula 10]

_{- [Al (R 24) -O} ] a -

In Formula 10, R ₂₄ is each independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;

[Formula 11]

D (R ₂₄ ) ₃

In Formula 11, D is aluminum or boron; Each R ₂₄ is independently as defined in Formula 10;

[Formula 12]

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

In Formula 12, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms, in which one or more hydrogen atoms may be substituted with a substituent; The substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryloxy having 6 to 20 carbon atoms.

The catalyst composition may include mixing and contacting a transition metal compound represented by Chemical Formula 1, a dialkylzinc compound represented by Chemical Formula 2, and a compound represented by Chemical Formula 10 or Chemical Formula 11 to obtain a mixture; And it may be prepared by a manufacturing method comprising the step of adding a compound represented by the formula (12) to the mixture.

Alternatively, the catalyst composition may include mixing and contacting a transition metal compound represented by Chemical Formula 1, a dialkylzinc compound represented by Chemical Formula 2, and a compound represented by Chemical Formula 12 to obtain a mixture. It can be manufactured by the manufacturing method.

When the transition metal compound represented by Formula 1 and the dialkyl zinc compound represented by Formula 2 and the compound represented by Formula 10 or Formula 11 are contacted to obtain a mixture, the transition metal compound represented by Formula 1 and the The molar ratio of the compound represented by Formula 10 or Formula 11 with respect to the dialkyl zinc compound represented by Formula 2 may be 1: 2 to 1: 5,000, and specifically 1:10 to 1: 1,000, More specifically, it may be 1:20 to 1: 500.

In addition, the molar ratio of the compound represented by Formula 12 to the transition metal compound represented by Formula 1 and the dialkyl zinc compound represented by Formula 2 may be 1: 1 to 1:25, and specifically 1: 1 to 1:10, and more specifically 1: 1 to 1: 5.

When the molar ratio of the transition metal compound represented by Chemical Formula 1 and the dialkyl zinc compound represented by Chemical Formula 2 to the compound represented by Chemical Formula 10 or 11 is less than 1: 2, the amount of the alkylating agent is very small. If the alkylation does not proceed completely and exceeds 1: 5,000, the alkylation of the metal compound is performed, but the activation of the alkylated metal compound is completely performed due to the side reaction between the remaining excess alkylating agent and the activator of Formula 12. There is a problem that cannot be supported. In addition, when the ratio of the compound represented by the formula (12) to the transition metal compound represented by the formula (1) and the dialkyl zinc compound represented by the formula (2) is less than 1: 1, the amount of the activator is relatively small, If the activation of the catalyst composition produced due to the incomplete activation is insufficient and exceeds 1:25, the metal compound is fully activated, but the excess amount of the remaining activator does not economically produce or produce the catalyst composition. There is a problem that the purity of the polymer is lowered.

In the preparation of the catalyst composition, when the transition metal compound represented by Formula 1 and the dialkyl zinc compound represented by Formula 2 and the compound represented by Formula 12 are contacted to obtain a mixture, The molar ratio of the transition metal compound and the compound represented by Formula 12 relative to the dialkyl zinc compound represented by Formula 2 may be 1: 1 to 1: 500, specifically 1: 1 to 1:50, More specifically, it may be 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activator is relatively small, so that the activation of the metal compound may not be completed, and thus the activity of the resulting catalyst composition may be inferior. Although completely made, there is a problem that the cost of the catalyst composition is not economically low or the purity of the resulting polymer is inferior with the remaining excess activator.

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

In addition, the transition metal compound represented by the formula (1), the dialkyl zinc compound represented by the formula (2) and the cocatalyst may be used in a form supported on a carrier. As the carrier, silica or alumina may be used.

The compound represented by Chemical Formula 10 is not particularly limited as long as it is alkylaluminoxane. Specific examples include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, or butyl aluminoxane, and more specific examples thereof include methyl aluminoxane.

The compound represented by Chemical Formula 11 is not particularly limited, but specific examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, and tri-s-butyl aluminum , Tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum Ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, or tributyl boron are mentioned, More specific examples are trimethyl aluminum, triethyl aluminum, or triisobutyl aluminum.

Examples of the compound represented by Formula 12 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N -Diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, dimethyl Aninium tetrakis (pentafluorophenyl) borate, triethylammonium tetraphenylaluminum, tributylammonium tetraphenylaluminum, tetra Methylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributyl Ammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N-diethylanilinium tetraphenylaluminum, N, N -Diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatentraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (p-tolyl) boron, triethyl Ammonium tetra (o, p-dimethylphenyl) boron, triphenylcarbonium tetra (p-trifluoromethylphenyl) boron or triphenylcarbo Tetra-pentafluoropropane, and the like phenylboronic.

A polyolefin homopolymer by contacting at least one olefin monomer with a catalyst composition comprising a transition metal compound of Formula 1, a dialkylzinc compound of Formula 2, and at least one compound selected from compounds represented by Formulas 10 to 12 Copolymers can be prepared.

The most preferable manufacturing process using the catalyst composition may be a solution process, and also when the catalyst composition is used together with an inorganic carrier such as silica, it is also applicable to a slurry or gas phase process.

In the preparation process, the activated catalyst composition is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, The solution may be dissolved or diluted in a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene. The solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.

Examples of the olefin monomer that can be polymerized using the metal compounds and the promoter include ethylene, alpha-olefin, cyclic olefin, and the like, and diene olefin monomers or triene olefin monomers having two or more double bonds. A monomer etc. can also superpose | polymerize. Specific examples of the monomers include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dode Sen, 1-tetradecene, 1-hexadecene, 1-ikocene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1, 5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc. are mentioned, These monomers can also be mixed and copolymerized.

In particular, in the preparation method of the present invention, the catalyst composition has a high molecular weight and has a high molecular weight of 0.91 g / cc or less in the copolymerization reaction of a monomer having high steric hindrance such as ethylene and 1-octene even at a high reaction temperature of 90 ° C. or higher. It is characterized in that the preparation of the coalescence is possible.

The polymer produced by the production method of the present invention may have a density of less than 0.91 g / cc, specifically less than 0.89 g / cc, and more specifically 0.885 g / cc or less.

In addition, the polymer prepared by the production method of the present invention has two melting temperatures (Tm) obtained from the DSC curve (Tm1 and Tm2), and therefore, thermal stability and mechanical strength because crystals are melted and crystallized at different temperatures, respectively. May increase.

The polymer prepared by the production method of the present invention may have a density of 0.85 to 0.91 g / cc, wherein the Tm1 is in the range of -30 to 90 ° C, and the Tm2 may be in the range of -10 to 95 ° C.

Specifically, the polymer produced by the manufacturing method of the present invention may have a density of 0.85 to 0.91 g / cc of the Tm1 in the range of 39 to 53 ℃, Tm2 may be in the range of 88 to 91 ℃.

As used herein, Tm means the temperature of the highest point of each peak in the temperature-heat flow graph of a differential scanning calorimetry (DSC).

In addition, the polymer prepared by the production method of the present invention has two crystallization temperatures (Tc) obtained from the DSC curve (Tc1 and Tc2), and therefore thermal stability and mechanical strength because crystals are melted and crystallized at different temperatures. Can increase

In the present specification, the crystallization temperature refers to the temperature at which crystallization occurs in which an irregular material structure is regularly changed in arrangement by molecular / atomic attraction, and can be analyzed by, for example, a differential scanning calorimeter (DSC). .

The polymer produced by the production method of the present invention may have a density of 0.85 to 0.91 g / cc, the Tc1 is in the range of 20 to 40 ℃, the Tc2 may be in the range of 50 to 80 ℃.

Specifically, the polymer prepared by the production method of the present invention may have a Tc1 in the range of 26 to 31 ° C and a Tc2 in the range of 56 to 67 ° C in a density range of 0.85 to 0.91 g / cc.

In addition, the polymer prepared by the production method of the present invention may have a Mw of 100,000 or more, specifically 100,000 to 1,000,000.

On the other hand, the polymer produced by the production method of the present invention may have a MWD of 3 or less, specifically 1 to 2.8, more specifically 1.5 to 2.5, more specifically may be 2 to 2.5.

According to one embodiment of the present invention, the polymer according to the present invention may have a MWD of 1 to 2.8, a Mw of 100,000 to 1 million, a density of less than 0.91 g / cc, specifically a MWD of 1.5 to 2.5, and a Mw of 100,000 to 1 million, and may have a density of less than 0.89 g / cc.

Hereinafter, the present invention will be described in more detail based on the following examples. These examples are provided to aid the understanding of the present invention, and the scope of the present invention is not limited thereto.

Organic reagents and solvents were purchased from Aldrich and purified by standard methods unless otherwise noted. At all stages of the synthesis, the contact between air and moisture was blocked to increase the reproducibility of the experiment. Among the ketone compounds represented by the formula (7), R 1 to R 6 are methyl compounds. Organometallics 2002, 21, 2842-2855].

Production Example

Preparation of Ligands and Transition Metal Compounds

8- (1,2-dimethyl-1H- Benzo [b] cyclopenta [d] thiophene -3- days) -2- methyl -1,2,3,4- Tetrahydroquinoline  (8- (1,2- dimethyl -1H- benzo [b] cyclopenta [d] thiophen -3- yl ) -2-methyl-1,2,3,4-tetrahydroquinoline) compound

To a solution of 2-methyl-1,2,3,4-tetrahydroquinoline (2 g, 13.6 mmol) in 10 mL of Ether was slowly added dropwise n BuLi (14.9 mmol, 1.1 eq) at -40 ° C. . After gradually raising the temperature to room temperature, the mixture was stirred at room temperature for 4 hours. The reaction was maintained at low temperature for 0.5 hours after injecting CO ₂ (g) having the temperature lowered to -40 ° C. After slowly warming up, the remaining CO ₂ (g) was removed through a bubbler. THF (17.6 mmol, 1.4 ml and t BuLi (10.4 mmol, 1.3eq) was injected at -20 ° C, and then aged at low temperature for 2 hours at -20 ° C. The ketone (1.9 g, 8.8 mmol) was converted to diethyl ether (Diethyl). ether) dissolved in a solution, and slowly added dropwise After stirring for 12 hours at room temperature, 10mL of water was added, hydrochloric acid (2N, 60mL) was added thereto, stirred for 2 minutes, organic solvent was extracted and neutralized with NaHCO ₃ aqueous solution. Extraction removed water with MgSO _{4. A} yellow oil was obtained through a silica gel column (1.83 g, 60% yield).

¹ H NMR (C ₆ D ₆ ): δ 1.30 (s, 3H, CH ₃ ), 1.35 (s, 3H, CH ₃ ), 1.89 to 1.63 (m, 3H, Cp-H quinoline-CH ₂ ), 2.62 to 2.60 (m, 2H, quinoline-CH ₂ ), 2.61-2.59 (m, 2H, quinoline-NCH ₂ ), 2.70-2.57 (d, 2H, quinoline-NCH ₂ ), 3.15-3.07 (d, 2H, quinoline-CH NCH ₂ ), 3.92 (broad, 1H, NH), 6.79 ~ 6.76 (t, 1H, aromatic), 7.00 ~ 6.99 (m, 2H, aromatic), 7.30 ~ 7.23 (m, 2H, aromatic), 7.54 ~ 7.53 ( m, 1H, aromatic), 7.62 ~ 7.60 (m, 1H, aromatic) ppm

8- (1,2-dimethyl-1H- Benzo [b] cyclopenta [d] thiophene -3- days) -2- methyl -1,2,3,4- Tetrahydroquinoline Titanium Dimethyl (8- (1,2- dimethyl -1H- benzo [b] cyclopenta [d] thiophen -3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline-titanium dimethyl) compound

N BuLi (3.0 mmol, 2.1 eq) was slowly added dropwise at −20 ° C. to the ligand (1.0 g, 2.89 mmol). It was observed that a yellow slurry (slurry) was formed, gradually warmed up to room temperature, and stirred at room temperature for 12 hours. TiCl ₄ DME (806 mg, 2.89 mmol, 1.0 eq) was added dropwise and stirred at room temperature for 12 hours. The solvent was removed and then extracted with toluene to give a red solid (700 mg, 52% yield). Methyl magnesium bromide (2.0 eq.) Was slowly added dropwise at room temperature to a solution of the red solid dissolved in 50 mL of THF, followed by stirring at room temperature for 12 hours, followed by removing the solvent and extracting with hexane to obtain a reddish brown solid (560 mg, 80% yield).

¹ H NMR (CDCl ₃ ) Mixture of two isomers: δ-7.1 (d, 1H, Ar-H), 6.84 (t, 1H, J = 7.5 Hz, Ar-H), 6.83 (t, 1H, J = 7.5 Hz, Ar-H), 6.98 (d, 1H, Ar-H), 2.6 ~ 2.7 (m, 2H, Piperidine-CH 2), 2.3 ~ 2.4 (m, 2H, Piperidine-CH 2), 1.63 ~ 1.69 ( m, 2H, Piperidine-CH ₂ ), 1.50-1.55 (m, 2H, Piperidine-CH ₂ ), 1.71-1.80 (m, 2H, Piperidine-CH ₂ ), 1.56-1.61 (m, 2H, Piperidine-CH ₂ ), 5.42 (m, 1H, Piperidine-CH), 1.15 (d, 3H, J = 6.5 Hz, Piperidine-CH ₃ ), 1.13 (d, 3H, J = 6.5 Hz, Piperidine-CH ₃ ), 7.84 (d , 1H, J = 8 Hz, Ar-H), 7.83 (d, 1H, J = 8 Hz, Ar-H), ~ 7.2 (t, 1H, Ar-H), 6.96 (t, 1H, Ar-H), 7.23 (d, 1H, J = 8 Hz, Ar-H), 7.25 (d, 1H, J = 8 Hz, Ar-H), 2.38 (s, 3H, Cp-CH ₃ ), 2.41 (s, 3H, Cp- CH ₃ ), 1.72 (s, 3H, Cp-CH ₃ ), 1.64 (s, 3H, Cp-CH ₃ ), 0.68 (s, 3H, Ti-CH ₃ ), 0.73 (s, 3H, Ti-CH ₃ ), 0.18 (s, 3H, Ti-CH ₃ ), 0.05 (s, 3H, Ti-CH ₃ ) ppm

Examples 1 to 4 and Comparative Example 1

Hexane solvent (1.0 L) and 1-octene (1.1 M) were added to the 2 L autoclave reactor, diethyl zinc was added in the amounts shown in Table 1 below, and the temperature of the reactor was preheated to 120 ° C. At the same time the reactor was pre-filled with ethylene to a pressure of 35 bar. The transition metal compound (8- (1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2, prepared in the above Preparation Example, wherein the reactor was treated with a triisobutylaluminum compound. -Methyl-1,2,3,4-tetrahydroquinoline-titanium dimethyl, 2.0 μmol) and dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) promoter (20 μmol) were applied in sequence under high pressure argon pressure. Into the reactor (molar ratio of Al: Ti = 10: 1). Subsequently, the copolymerization reaction proceeded for 8 minutes. Next, the remaining ethylene gas was removed and the polymer solution was added to excess ethanol to induce precipitation. The precipitated polymer was washed two to three times with ethanol and acetone, and then dried in an 80 ° C. vacuum oven for at least 12 hours to measure physical properties.

Physical property evaluation (weight, activity, melt index, melting point, density)

The melt index (Melt Index, MI) of the polymer was measured by ASTM D-1238 (Condition E, 190 ° C., 2.16 Kg load). The melting point (Tm) of the polymer was obtained using a differential scanning calorimeter (DSC: Differential Scanning Calorimeter 2920). That is, the temperature is 200 After increasing to ℃, keep at that temperature for 5 minutes and then 30 The temperature was lowered to < RTI ID = 0.0 > C, < / RTI > At this time, the rate of rise and fall of temperature is 10 ℃ / min, melting point was obtained while the second temperature was rising. In addition, the density of the polymer is 180 A sheet having a thickness of 3 mm and a radius of 2 cm was made with a press mold, and cooled to 10 ° C./min and measured on a Mettler balance.

Physical properties of the polymers prepared in Examples 1 to 4 and Comparative Example 1 are shown in Table 1 below.

Transition metal compound
(μmol) Diethyl
zinc
(μmol) yield
(Kg / mmolTi) density
(g / cc) Melt index
(g / 10min) Tc
(℃)
Tm
(℃)
MWD Example 1 2 20 41 0.870 0.08 29.0 /
66.3 39.5 /
88.3 2.41 Example 2 2 40 41 0.872 0.07 29.3 /
58.7 51.8 /
90.0 2.39 Example 3 2 100 39 0.871 0.03 30.4 /
64.4 52.5 /
90.7 2.35 Example 4 2 200 30 0.872 0.11 27.7 /
56.5 51.1 /
89.8 2.01 Comparative Example 1 2 - 49 0.872 0.10 29.1 /
68.5 38.9 /
89.0 3.29

Polymerization conditions: Hexane (1.0 L), ethylene (35 bar), 120 ° C., Promoter AB 10 equivalents, 1-C ₈ 1.1 (mol / L), *: 1-C ₈ 1.47 (mol / L), t = 8 min, Tc: crystallization temperature, Tm: melting temperature, MWD: molecular weight distribution (weight average molecular weight / number average molecular weight)

As shown in Table 1, the polymer prepared using the catalyst compositions of Examples 1 to 4 compared to the comparative example was able to form a polymer having a low density region while having a narrow molecular weight distribution and excellent copolymerizability.

Claims (18)

To include a transition metal compound of Formula 1 and a dialkyl zinc compound of Formula 2,
The catalyst composition of the dialkyl zinc compound of Formula 2 is mixed in an amount of 10 to 100 equivalents to 1 equivalent of the transition metal compound of Formula 1:
[Formula 1]

[Formula 2]

In Chemical Formula 1,
M is a Group 4 transition metal,
Q ₁ and Q ₂ are each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms,
R ₁ to R ₆ are each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms,
R ₇ to R ₉ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two of R ₇ to R _{9 may} be linked to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
Cy is a 5 or 6 membered aliphatic ring,
R, R ₁₆ and R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, an integer of 0 to 4 when Cy is a 6-membered aliphatic ring,
In Chemical Formula 2,
R ₁₈ and R _{19 's} are each independently alkyl having 1 to 20 carbon atoms.
The method of claim 1,
The compound of Formula 1 is a catalyst composition which is a compound represented by the following formula (3) or:
[Formula 3]

In Chemical Formula 3, R ₁₂ to R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
The remaining substituents are the same as in Formula 1
[Formula 4]

In Chemical Formula 4,
R ₂₀ to R ₂₃ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,
The remaining substituents are the same as in formula (1).
The method of claim 1,
R ₁ and R ₂ is a catalyst composition having 1 to 20 carbon atoms alkyl.
The method of claim 1,
M is Ti, Hf or Zr catalyst composition.
The method of claim 1,
The compound represented by Formula 1 is a catalyst composition which is a compound represented by any one of the following formula:
(i)

(ii)

(iii)

(iv)

(v)

(vi)

(vii)

The method of claim 1,
The dialkyl zinc compound of Formula 2 is at least one selected from the group consisting of diethyl zinc, dipropyl zinc, dibutyl zinc and ethyl propyl zinc, catalyst composition.
delete The method of claim 1,
Catalyst composition wherein the catalyst composition further comprises one or more cocatalysts.
The method of claim 8,
The promoter is a catalyst composition comprising one or more selected from the following formula 10 to 12.
[Formula 10]
_{- [Al (R 24) -O} ] a -
In Formula 10, R ₂₄ is each independently a halogen radical; Hydrocarbyl radicals having 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen; a is an integer of 2 or more;
[Formula 11]
D (R ₂₄ ) ₃
In Formula 11, D is aluminum or boron; Each R ₂₄ is independently as defined in Formula 10;
[Formula 12]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
In Formula 12, L is a neutral or cationic Lewis acid; H is a hydrogen atom; Z is a Group 13 element; A is each independently aryl having 6 to 20 carbon atoms or alkyl having 1 to 20 carbon atoms, in which one or more hydrogen atoms may be substituted with a substituent; The substituent is halogen, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryloxy having 6 to 20 carbon atoms.
The catalyst composition of claim 1, wherein the catalyst composition further comprises a reaction solvent.
A supported catalyst, wherein the catalyst composition according to claim 1 is supported on a carrier.
Method for producing a polymer using the catalyst composition according to claim 1.
The method of claim 12,
Wherein said polymer is a homopolymer or copolymer of polyolefins.
A method for producing a polymer using the supported catalyst according to claim 11.
The method of claim 14,
Wherein said polymer is a homopolymer or copolymer of polyolefins.
delete delete delete