KR0169764B1 - Metallocene catalyst for olefin polymerization - Google Patents

Abstract

The present invention relates to a olefin, cycloolefin, diene, vinyl monomer of a titanium, zirconium, hafnium or lanthanide-based metal compound supported on a styrene-divinylbenzene copolymer using a ligand compound in which a cycloalkanedinyl derivative is bonded to silicon. The present invention relates to a metallocene catalyst used for the polymerization and a process for producing the same.

Description

Metallocene Catalysts for Olefin Polymerization

The present invention relates to a metallocene catalyst for olefin polymerization prepared by supporting a metal compound on a styrene-divinylbenzene copolymer.

More specifically, an olefin, cycloolefin, diene supported on a styrene-divinylbenzene copolymer using a ligand compound in which a titanium, zirconium, hafnium, or lanthanide-based metal compound is substituted with a cycloalkanedienyl derivative substituted with silicon. The present invention relates to a metallocene catalyst used for polymerization of vinyl monomers and a method for producing the same.

Generally, a Ziegler-Natta catalyst has been widely used as a catalyst for olefin polymerization. The Ziegler-Natta catalyst is a transition metal compound mainly a titanium halide compound (for example titanium tetrachloride) as the main catalyst, alkyl aluminum (for example trimethylaluminum or triethylaluminum) as the cocatalyst. However, in order to obtain a polymer having high activity and improved physical properties in the catalyst, changes in the catalyst system and improvement of the reaction process have been actively attempted. One such attempt has been to develop heterogeneous catalysts through the support of catalysts.

Supporting the catalyst is a technique for depositing the catalyst on the modified surface of organic compounds (for example, silica, magnesium chloride, alumina, etc.) or organic compounds, which is a copolymer of ethylene and alpha olefins (propylene, butene, hexene, etc.). It is widely used in the production of linear low density polyethylene (LLDPE). In this related US Pat. No. 4,137,547, an organic-aluminum compound and an organic-magnesium compound are used as a carrier, and a tetravalent titanium compound is used as a supported catalyst for olefin polymerization together with a promoter alkylaluminum compound. That is, it was a method of supporting by chemical reaction between a hydroxyl group and titanium tetrachloride on the surface of the silica carrier.

Recently, metallocene-based catalysts have been developed for improved LLDPE production. Metallocene catalysts have a central metal transition metal group IVB compound (titanium, zirconium, hafnium) and ligands having 1 to 2 cycloalkanedienyl compounds (e.g., cyclopentadiene, indene, fluorene ( Fluorene, etc.] has a structure bonded in the form of a sandwich, and as a promoter, unlike the previous Ziegler-Natta catalyst, alkyl aluminum oxane (for example, methyl aluminum oxane), which is a reactant of water and an alkyl aluminum compound, Used.

Metallocene catalysts have been found to be more effective in preparing polymers with higher activity and stereoregularity than Ziegler-Natta based catalysts. In European Patent Nos. 294,942 and 313,386, the metallocene catalyst was supported on various inorganic compounds (silica, alumina, etc.) and applied to polyolefin production.

In addition, in addition to the inorganic carriers mentioned above, as a technology related to organic carriers, Russian Patent No. 682,262 used polypropylene-polyethylene particles having an inert surface as a carrier and vinyl alcohol-ethylene copolymer having a reactor, and in Russian Patent No. 1,886,351 Polystyrene and polystyrene-divinylbenzene copolymers were used as carriers, and vanadium tetrachloride was reacted with a benzene ring of styrene to be supported by an activating catalyst in the form of vanadium trichloride, and subjected to olefin polymerization.

US Pat. No. 4,808,561 also describes improved polymer production by using styrene-divinylbenzene as a support and controlling the pore size and crosslinking volume of the substrate by varying the content of comonomer divinylbenzene. The catalyst used was a Ziegler-Natta type catalyst.

In the present invention, the above-described styrene-divinylbenzene copolymer as a support to support a metallocene catalyst having excellent activity and performance, and invented a catalyst for olefin polymerization using alkylaluminum oxane as a promoter, It is possible to control the pore size and the crosslinking volume of the carrier by using organic carriers than in the case of the conventional inorganic carrier.It is a new method of supporting metallocene catalysts by staged chemical reactions, unlike conventional simple supporting methods. It is possible to support a strong catalyst to obtain a polymer of improved physical properties.

Hereinafter, the method for preparing the metallocene catalyst supported on the styrene-divinylbenzene copolymer prepared in the present invention is as follows.

Preparing a ligand compound of formula (II) in which a halogen or methyl is bonded to a cycloalkanedienyl compound centered on silicon (Si);

In the formula, A is a halogen atom, lower alkyl group having 1 to 6 carbon atoms,

Phenoxy or lower alkoxy having 1 to 6 carbon atoms,

X is a halogen atom, lower alkoxy or phenoxy having 1 to 6 carbon atoms,

M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( ) Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in a benzene ring of an indene group or a fluorene group.

The meta or para position of the benzene ring of the styrene-divinylbenzene copolymer is ionized with a strong base containing metals such as Li, Na, K, Mg and the like to activate the benzene ring, and, if necessary, the Friedel-Craft reaction is applied to the benzene ring. Activating after alkylation;

The activated styrene-divinylbenzene copolymer is reacted with a ligand compound of general formula (II), and a metal compound and metal including a group IVB transition metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71 A metallocene catalyst supported on the styrene-divinylbenzene copolymer of the present invention represented by general formula (I) a, (I) b or (I) c is prepared by metallization reaction.

In the above formula

R1 and R2 are each an alkyl group having 1 to 6 carbon atoms;

M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group;

Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71;

X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms.

Of the catalytic compounds represented by the general formula (I) a, preferred compounds are those wherein Me is zirconium, M and N are indene, and X is chlorine.

Among the catalytic compounds represented by general formula (I) b, preferred compounds are those in which Me is zirconium, M and N are indenes, R 1 is a methyl group, and X is chlorine.

Finally, among the catalytic compounds represented by the general formula (I) c, preferred compounds are when z is zirconium, M and N are indene, R 1 is methyl group, R 2 is isopropyl group, and X is chlorine. .

The catalyst prepared by the above method is used in the olefin polymerization reaction by adding an alkyl aluminum oxane compound, preferably methyl aluminum oxane, in an amount of 5 to 2,000 moles of cocatalyst to 1 mole of catalyst as a cocatalyst. At this time, the preferred amount of promoter is 50 to 2,000 moles.

Monomers which can be polymerized with the catalyst of the present invention are α-olefins, cycloolefins, dienes, vinyl monomers and the like.

Hereinafter, the present invention will be described in more detail with the following examples. However, the scope of the present invention is not limited to the following examples. In the following examples, the content of catalyst and cocatalyst component, catalytic activity and melting point were determined by the following method.

(1) content of metal components

0.5 g of the supported catalyst was decomposed with nitric acid and diluted with distilled water to obtain a sample solution. The amount of zirconium contained in this solution was analyzed by an Inductively Coupled Plasma Spectrophotometer (ICP) to determine its content.

(2) activity of the catalyst

The weight of the polymer obtained in the polymerization was measured to show catalytic activity as Kg-Polymer / mol-Zr-atm.

(3) melting point

About 6 mg of sample was placed in an aluminum pan and the melting point was determined using a DuPont 2000 system (DSC) under a nitrogen atmosphere. The temperature increase temperature was 10 degrees C / min.

Example 1

[Synthesis of Carrier]

50 g of styrene-divinyl benzene copolymer (weight average molecular weight 150,000) containing 5% of divinyl benzene was added to 100 g of toluene, and then 6 g of normal butyllithium and 0.5 g of tetramethylethylenediamine (TMEDA) were added thereto. The reaction was carried out to a copolymer of a crosslinked lithium salt state.

[Synthesis of ligands]

100 g of toluene was added to 25 g of indene, 37 g of normal butyllithium was added at -50 ° C, and reacted for 12 hours to synthesize the indene-lithium salt. 13 g of tetrachloride silane was added thereto and reacted at room temperature for 5 hours to synthesize bisindenedichlorosilane.

[Synthesis of Catalyst]

100 g of the synthesized carrier was added to 500 g of tetrahydrofuran, and then 86 g of normal butyllithium was added dropwise, followed by reaction at -50 ° C. for 8 hours, followed by filtration and purification, followed by further 500 g of tetrahydrofuran and 75 g of zirconium tetrachloride (ZrCl 4.2 THF) and reacted at room temperature for 12 hours to synthesize catalyst (I) a having the structure of Formula (I) a.

[Polymerization reaction]

The polymerization was carried out in an external temperature controller, a magnetic stirrer, and a glass reactor with a valve capable of supplying monomers and nitrogen. Into a sufficiently nitrogen-substituted reactor, 300 ml of purified toluene and 10 mmol MAO, 100 mg of the catalyst prepared above were mixed, propylene was injected to a reaction pressure, and then reacted at 40 ° C. for 6 hours. After 6 hours, 50 ml of hydrochloric acid-ethanol mixed solution was added to terminate the reaction, and the polymer was purified six times with methanol for 12 hours. The polymer obtained was vacuum dried at 60 ° C. for 24 hours.

[Copolymerization reaction]

It carried out in the same glass reactor as the polymerization apparatus described above. In a nitrogen-substituted reactor, 300 ml of purified toluene, 5 ml MAO, and 0.09 g of the catalyst prepared above were mixed, 13.46 mmol of propylene was injected, and ethylene was injected to the reaction pressure (3 atm) while the reaction was carried out at 70 ° C., 6 Let time. After 6 hours, 50 ml of hydrochloric acid-ethanol mixed solution was added to terminate the reaction, and the polymer was purified six times with methanol for 12 hours. The polymer obtained was vacuum dried at 60 ° C. for 24 hours.

Example 2

[Synthesis of Carrier]

It prepared in the same manner as in Example 1.

[Synthesis of ligands]

The ligand was prepared in the same manner as in Example 1, except that 16 g of 1-methyl trichloride silane was used instead of tetrachloride silane.

[Synthesis of Catalyst]

Prepared in the same manner as in Example 1 to synthesize a catalyst (I) b having the structure of general formula (I) b.

[Polymerization reaction]

The polymerization reaction was carried out in the same manner as in Example 1.

[Copolymerization reaction]

The polymerization reaction was carried out in the same manner as in Example 1.

Example 3

[Synthesis of Carrier]

100 g of styrene-divinylbenzene copolymer (weight average molecular weight 150,000) containing 5% divinylbenzene was added 500 g of toluene, aluminum trichloride containing isopropane and aluminum trichloride, and then Friedel-Craft (Fiedel-) Craft) After the acylation reaction, it is filtered and dried. The subsequent manufacturing method is the same as in Example 1.

[Synthesis of ligands]

Prepared in the same manner as in Example 2.

[Synthesis of Catalyst]

Prepared in the same manner as in Example 1 to synthesize a catalyst (I) c having the structure of formula (I) c.

[Polymerization reaction]

The polymerization reaction was carried out in the same manner as in Example 1.

[Copolymerization reaction]

The polymerization reaction was carried out in the same manner as in Example 1.

Comparative Example 1

[Catalyst Synthesis]

A homogeneous catalyst, excluding the support (polystyrene-divinylbenzene copolymer) portion of the catalyst (I) a synthesized in Example 1, was synthesized according to Example 1.

[Catalytic support]

Silica (Davison Grade 952), which was dried at 600 ° C. for 10 hours, was dispersed in toluene, and the above catalyst dissolved in toluene at room temperature was added, and the mixture was reacted at 70 ° C. for 15 hours, washed with toluene, and then a silica supported catalyst ( II) a was synthesized.

[Polymerization reaction]

It carried out by the same method as Example 1 using catalyst (II) a.

[Copolymerization reaction]

It carried out by the same method as Example 1 using catalyst (II) a.

Comparative Example 2

[Catalyst Synthesis]

A homogeneous catalyst, excluding the support (polystyrene-divinylbenzene copolymer) portion of catalyst (I) b synthesized in Example 2, was synthesized according to Example 2.

[Catalytic support]

Silica (Davison Grade 952), which was dried at 600 ° C. for 10 hours, was dispersed in toluene, and the above catalyst dissolved in toluene at room temperature was added, and the mixture was reacted at 70 ° C. for 15 hours, washed with toluene, and then a silica supported catalyst ( II) b was synthesized.

[Polymerization reaction]

It carried out by the same method as Example 2 using catalyst (II) b.

[Copolymerization reaction]

It carried out by the same method as Example 2 using catalyst (II) b.

Comparative Example 3

[Catalyst Synthesis]

A homogeneous catalyst in which the supported (polystyrene-divinylbenzene copolymer) portion of the catalyst (I) c synthesized in Example 3 was excluded was synthesized according to Example 3.

[Catalytic support]

Silica (Davison Grade 952), which was dried at 600 ° C. for 10 hours, was dispersed in toluene, and the above catalyst dissolved in toluene at room temperature was added, and the mixture was reacted at 70 ° C. for 15 hours, washed with toluene, II) c was synthesized.

The polymerization and copolymerization results of the catalysts prepared in Examples and Comparative Examples are as follows.

Claims (7)

Preparing a ligand compound of formula (II) in which a halogen or alkyl is bonded to a cycloalkanedienyl compound mainly on silicon (Si); Wherein A is a halogen atom, a lower alkyl group of 1 to 6 carbon atoms, phenoxy or lower alkoxy of 1 to 6 carbon atoms, X is a halogen atom, lower alkoxy or phenoxy of 1 to 6 carbon atoms, and M and N are each cyclo Pentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group. The meta or para position of the benzene ring of the styrene-divinylbenzene copolymer is ionized with a strong base containing metals such as Li, Na, K, Mg, and the like, and activated if necessary, and subjected to a Friedel-Craft reaction on the benzene ring. Activating after alkylation; The activated styrene-divinylbenzene copolymer is reacted with a ligand compound of general formula (II), and a metal compound and metal including a group IVB transition metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71 Process for preparing metallocene catalyst compound supported on styrene-divinylbenzene copolymer represented by formula (I) a characterized in that the reaction In the above formula, M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group; Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71; X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms. Metallocene catalyst compound for olefin polymerization represented by general formula (I) a In the above formula, M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( ) Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group; Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71; X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms. [Claim 3] The metallocene catalyst compound of claim 2, wherein the catalyst compound of formula (I) a has Me as zirconium, M and N as indenes, and X as chlorine. Preparing a ligand compound of formula (II) in which a halogen or alkyl is bonded to a cycloalkanedienyl compound mainly on silicon (Si); Wherein A is a halogen atom, a lower alkyl group of 1 to 6 carbon atoms, phenoxy or lower alkoxy of 1 to 6 carbon atoms, X is a halogen atom, lower alkoxy or phenoxy of 1 to 6 carbon atoms, and M and N are each cyclo Pentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group. The meta or para position of the benzene ring of the styrene-divinylbenzene copolymer is ionized with a strong base containing metals such as Li, Na, K, Mg and the like, and activated in a benzene ring in a Friedel-Craft reaction if necessary. Activating after alkylation; The activated styrene-divinylbenzene copolymer is reacted with a ligand compound of general formula (II), and a metal compound and metal including a group IVB transition metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71 Method for preparing metallocene catalyst compound supported on styrene-divinylbenzene copolymer represented by formula (I) b characterized in that the reaction R <1> is a C1-C6 alkyl group in said Formula; M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group; Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71; X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms. Metallocene catalyst compound for olefin polymerization represented by general formula (I) b R <1> is a C1-C6 alkyl group in said Formula; M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group; Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71; X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms. Preparing a ligand compound of formula (II) in which a halogen or alkyl is bonded to a cycloalkanedienyl compound mainly on silicon (Si); Wherein A is a halogen atom, a lower alkyl group of 1 to 6 carbon atoms, phenoxy or lower alkoxy of 1 to 6 carbon atoms, X is a halogen atom, lower alkoxy or phenoxy of 1 to 6 carbon atoms, and M and N are each cyclo Pentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group. The meta or para position of the benzene ring of the styrene-divinylbenzene copolymer is ionized with a strong base containing metals such as Li, Na, K, Mg, and the like, and activated if necessary, and subjected to a Friedel-Craft reaction on the benzene ring. Activating after alkylation; The activated styrene-divinylbenzene copolymer is reacted with a ligand compound of general formula (II), and a metal compound and metal including a group IVB transition metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71 Method for preparing metallocene catalyst compound supported on styrene-divinylbenzene copolymer represented by formula (I) c characterized in that the reaction In the above formula, R1 and R2 are each an alkyl group having 1 to 6 carbon atoms; M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group; Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71; X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms. Metallocene catalyst compound for olefin polymerization represented by general formula (I) c In the above formula, R1 and R2 are each an alkyl group having 1 to 6 carbon atoms; M and N are each cyclopentadiene group ( ), Indengi ( ), Fluorene group ( Or an indene derivative or fluorene derivative in which 1 to 3 alkyl groups of 1 to 4 carbon atoms are substituted in the benzene ring of the indene group and the fluorene group; Me is a group IVB metal (zirconium, titanium, hafnium) or a lanthanide metal having an atomic number of 58 to 71; X is a halogen atom such as chlorine or bromine, lower alkoxy or phenoxy having 1 to 6 carbon atoms.