KR101631702B1 - Catalyst for olefin polymerization and preparation method of polyolefin by using the same - Google Patents

Abstract

The present invention relates to a catalyst for olefin polymerization capable of providing various selectivity and high activity for a polyolefin copolymer, and is characterized in that an anisometallocene compound having a novel structure is supported together with an alkyl aluminoxane promoter and a boron promoter And a process for producing a polyolefin using the same.
The catalyst for olefin polymerization of the present invention always exhibits high activity irrespective of the kind and state of the carrier, the amount of supported metallocene compound, and the temperature and time during the supporting reaction.

Description

TECHNICAL FIELD [0001] The present invention relates to a catalyst for olefin polymerization and a process for producing polyolefin using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a catalyst for olefin polymerization capable of providing various selectivity and high activity for a polyolefin copolymer.

The ansa-metallocene compound is an organometallic compound containing two ligands connected to each other by a bridge group, in which the rotation of the ligand is prevented by the bridge group, The structure is determined.

These anisometallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, it is known that an anisometallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, thereby controlling the microstructure of the polypropylene have. It is also known that an anhydride-metallocene compound containing an indenyl ligand can produce a polyolefin having excellent activity and improved stereoregularity.

In this way, when the anthra-metallocene compound capable of controlling the microstructure of the olefin polymer is used in a practical commercialized gas phase and slurry plant, the carrier is supported. Studies have been made to carry out co-catalysis at the same time to carry out the catalytic reaction and to exhibit activity without addition of additional co-catalyst during the polymerization process. However, if a non-homogeneous catalyst is prepared by carrying out basically, The activity becomes lower than that of the homogeneous catalyst.

In order to overcome this problem, various attempts have been made to carry out a method for improving the activity, but the degree of the method is still insufficient.

In order to improve the activity as a supported catalyst, the present invention aims to provide a catalyst for olefin polymerization which can exhibit high activity by supporting an anisometallocene compound having a novel structure together with two kinds of optimal promoters.

The present invention also provides a process for producing a polyolefin using the supported catalyst.

The present invention is to provide an olefin polymerization catalyst comprising an anhydride-metallocene compound represented by the following formula (1), an alkylaluminoxane-based promoter, and a boron-based promoter.

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

A is a bridge group connecting an indenyl group as an element of Group 14;

R ¹ is alkyl, alkenyl, alkylaryl, arylalkyl or aryl of 1 to 20 carbon atoms;

R ² is hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;

R ³ , R ^{3 '} , R ⁴ , and R ^4' are the same or different from each other and are each an alkyl, alkenyl, alkylaryl, arylalkyl, or aryl having 1 to 20 carbon atoms;

n is an integer of 1 to 20;

The present invention also provides a process for producing a polyolefin using the supported catalyst.

Hereinafter, a catalyst for olefin polymerization according to a specific embodiment of the present invention and a method for producing a polyolefin using the same will be described in detail. It is to be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

In addition, throughout this specification, "comprising" or "containing ", unless specifically stated, refers to including any and all components (or components) Can not be interpreted as excluding.

The present inventors have repeatedly studied metallocene compounds. In the process of repeatedly studying metallocene compounds, the present inventors have found that when an indenyl group in which substituents other than hydrogen are introduced at positions 2 and 4 are used as ligands and a bridge group an anthra-metallocene compound having a functional group capable of acting as a Lewis base was substituted for an oxygen-donor in a bridge group was prepared. The compound was supported on a carrier using the catalyst precursor as a catalyst precursor It has been confirmed that polypropylene having higher activity can be produced when two kinds of co-catalysts are carried simultaneously and when the optimum amount of used catalyst is carried, than that of carrying one kind of co-catalyst, Completed.

According to one embodiment of the present invention, there is provided an olefin polymerization catalyst comprising an anhydride-metallocene compound represented by the following formula (1), an alkylaluminoxane-based promoter, and a boron-based promoter.

[Chemical Formula 1]

In Formula 1,

M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;

X is the same or different halogen;

A is a bridge group connecting an indenyl group as an element of Group 14;

R ¹ is alkyl, alkenyl, alkylaryl, arylalkyl or aryl of 1 to 20 carbon atoms;

R ² is hydrogen, alkyl of 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;

R ³ , R ^{3 '} , R ⁴ , and R ^4' are the same or different from each other and are each an alkyl, alkenyl, alkylaryl, arylalkyl, or aryl having 1 to 20 carbon atoms;

and n may be an integer of 1 to 20.

Preferably, R ¹ and R ² in the general formula (1) are each alkyl having 1 to 4 carbon atoms; R ³ and R ^{3 '} are each alkyl, alkenyl, or arylalkyl having 1 to 20 carbon atoms; R ⁴ and R ^{4 '} are each aryl or alkylaryl of 1 to 20 carbon atoms; n is an integer from 1 to 6; A may be silicon (Si).

The anthese-metallocene compound of Formula 1 includes two indenyl groups as a ligand, and in particular, an oxygen-donor is added to a bridge group connecting the ligand to form an Lewis base Functional group capable of acting as a substituent is substituted, thereby maximizing the activity as a catalyst. Accordingly, when the compound of Formula 1 is supported on its own or on a carrier and used as a catalyst in the production of polyolefins, a polyolefin having desired physical properties can be more easily produced.

The catalyst for olefin polymerization according to the present invention is a catalyst in which the anisometallocene compound, the alkylaluminoxane-based co-catalyst, and the boron-based co-catalyst are supported on a carrier. The carrier may be any of those generally used in the technical field to which the present invention belongs, so that it is not particularly limited, but preferably at least one carrier selected from the group consisting of silica, silica-alumina and silica-magnesia may be used. On the other hand, when supported on a support such as silica, since the silica carrier and the functional groups of the anisole-metallocene compound are chemically bonded and supported, there is almost no catalyst liberated from the surface of the support in the olefin polymerization process, There is no fouling that is entangled in the reactor wall surface or the polymer particles.

In addition, the polyolefin produced in the presence of such a silica carrier-containing catalyst is excellent in the particle shape and bulk density of the polymer, and can be suitably used in conventional slurry polymerization, bulk polymerization and gas phase polymerization processes.

Therefore, it is preferable to use a carrier which is dried at a high temperature and has a siloxane group having high reactivity on the surface. Specifically, silica, silica was dried at high temperature - can be used are alumina and the like, which are typically _{Na 2 O, K 2 CO 3} , BaSO 4, Mg (NO 3) an oxide of _2, such as carbonate, sulfate, nitrate component .

In the present invention, the anisometallocene compound is used as a catalyst precursor, together with an alkylaluminoxane-based promoter and a boron-based promoter, as a catalyst for olefin polymerization.

In the catalyst for olefin polymerization, the promoter composed of alkylaluminoxane may be represented by the following formula (2).

(2)

In Formula 2,

M ² is a Group 13 metal element;

R ⁵ are the same or different and are each an alkyl, alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;

m may be an integer of 2 or more.

The alkylaluminoxane-based promoter is preferably a compound wherein R ⁵ in the above formula 2 is methyl, ethyl, propyl, isopropyl, isopropenyl, n- butyl (n-butyl), sec- butyl (sec -butyl), tert- butyl (tert -butyl), pentyl (pentyl), hexyl (hexyl), octyl (octyl), decyl (decyl), dodecyl (dodecyl) Tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, eikosyl, dokosyl, tetrakosyl, cyclododecyl, cyclohexyl, Cyclohexyl, cyclooctyl, phenyl, tolyl, or ethylphenyl; M ² may be aluminum.

In Formula 2, m may be an integer of 2 or more, or an integer of 2 to 500, preferably 6 or more, or an integer of 6 to 300, more preferably 10 or more, or an integer of 10 to 100.

The alkylaluminoxane-based co-catalyst may be a compound capable of acting as a Lewis acid capable of forming a bond through a Lewis acid-base interaction with a functional group introduced into a bridge group of the metallocene compound of Formula 1 And a metal element. The promoter compound of Formula 2 may exist in a linear, circular or network form. Examples of the promoter compound include at least one of methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane and butyl aluminoxane. have.

In the catalyst for olefin polymerization of the present invention, a co-catalyst containing a non-conjugated anion as a non-alkylaluminoxane-based catalyst may be used together with the alkylaluminoxane-based co-catalyst. In particular, in the present invention, a boron-based promoter may be used as the non-alkylaluminoxane-based co-catalyst. The boron-based promoter may be selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, [HN (CH ₃ ) ₂ C ₆ H ₅ ] [B (C ₆ F ₅ ) ₄ ] ), Trityl tetakis (pentafluorophenyl) borate, [(C ₆ H ₅ ) ₃ C] [B (C ₆ F ₅ ) ₄ ]), and methyl anilinium tetrakis (Pentafluorodiphenyl) borate, [HN (CH ₃ ) (C ₆ H ₅ ) ₂ ] [B (C ₆ F ₅ ) ₄ ] Can be used.

The boron-based promoter enables stabilization of the anisometallocene compound of the present invention to maintain activity in polymerization. Especially. The catalyst precursor used in the present invention is a tether, and leaching phenomenon does not occur during polymerization due to this functional group, so fouling does not occur and excellent activity can be exhibited. However, if there is no tether such as a known metallocene compound, there is a problem that fouling occurs mostly due to reaction with a leached catalyst precursor and a boron-based co-catalyst.

In the present invention, two supported catalysts, that is, an alkylaluminoxane-based promoter and a non-alkylaluminoxane-based boron-based promoter, are simultaneously carried to form a supported catalyst having improved activity. Also, the co-catalysts which did not cause adverse effects between the two co-catalysts were selected, and the optimum supporting ratio was confirmed through experiments.

In the catalyst for olefin polymerization of the present invention, the anisometallocene compound may be supported in an amount of 40 to 240 μmol, preferably 80 to 160 μmol, based on 1 g of silica per weight of carrier, in terms of 1 g of silica. In addition, the alkylaluminoxane-based co-catalyst may be supported in an amount of 8 to 25 mmol, preferably 10 to 20 mmol, based on 1 g of silica per weight of carrier, for example. The boron-containing promoter may be supported in an amount ranging from 50 to 300 μmol, preferably from 64 to 240 μmol, based on 1 g of silica per weight of carrier, for example, 1 g of silica. On the other hand, in the catalyst for olefin polymerization of the present invention, the molar ratio of the boron-based promoter to the anisometallocene compound may be 0.1 to 3.0, preferably 0.2 to 2.0, more preferably 0.3 to 1.4, Can be from 0.5 to 1.2.

The catalyst for olefin polymerization according to the present invention basically has an improved catalytic activity over that of a supported catalyst carrying one kind of promoter, and even if the supporting condition of the anisometallocene compound is changed, that is, the reaction temperature, the reaction time, , It is possible to produce a supported catalyst capable of producing polypropylene having improved activity even when the amount of supported anthese-metallocene compound is changed.

According to another embodiment of the present invention, there is provided a process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the catalyst for olefin polymerization.

The olefin monomer may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-octadecene, 1-eicosene, and mixtures thereof.

Here, the polymerization of the polyolefin may be carried out by reacting at a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm ² for 1 to 24 hours. At this time, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 50 to 100 ° C. The polymerization reaction pressure is preferably 1 to 70 kgf / cm ² , more preferably 5 to 50 kgf / cm ² . The polymerization reaction time is preferably 1 to 5 hours.

As described above, when the catalyst for olefin polymerization comprising the two promoters of the present invention is calculated by the ratio of the weight (kg) of the polymer produced per unit weight (g) of the catalyst unit used based on the unit time (h) , The activity of the supported catalyst having only one kind of cocatalyst can be improved by more than 40%. And more preferably by 45% or more.

The catalyst for olefin polymerization according to the present invention can produce a polyolefin having a higher molecular weight than that of the conventional metallocene compound by using the anisometallocene compound. In particular, when the polymerization process is carried out under the condition that hydrogen is not added using the anisotropic metallocene compound according to the present invention, the resulting polyolefin has a weight average molecular weight (Mw) of 200,000 or more, or 200,000 to 600,000, May be at least 250,000, and more preferably at least 300,000. In addition, according to the present invention, when the polymerization process is carried out under the condition of adding hydrogen using the anthra-metallocene compound according to the present invention, the polymerization process is performed under the condition of, for example, adding 0.37 L of hydrogen under 1 atm of the reactor condition , The resulting polyolefin may have a weight average molecular weight (Mw) of 90,000 or less, or 55,000 to 90,000, preferably 85,000 or less, more preferably 80,000 or less.

As described above, the catalyst for olefin polymerization according to the present invention can be produced by effectively selecting a low molecular weight or high molecular weight polyolefin by controlling the hydrogenation amount of the polymerization process using the anisometallocene compound.

The polyolefin thus prepared may have a molecular weight distribution (Mw / Mn) of 3.5 or less, or 1 to 3.5, preferably 3.0 or less, such as 1.5 to 3.0 or 2.0 to 3.0.

As described above, the catalyst for olefin polymerization according to the present invention has a catalyst activity of 20 kg / mmol ㆍ calculated by the ratio of the weight (kg) of the produced polymer per mol of catalyst unit (mmol) hr or 20 to 160 kg / mmol · hr, preferably 50 kg / mmol · hr or more, more preferably 70 kg / mmol · hr or more, or 92 kg / mmol · hr or more. Further, the activity of the catalyst is preferably 1.0 kg / gCat 占 이상 r or more, or 1.0 to 10 占 폚, when calculated as a ratio of the weight (kg) of the polymer produced per gram of the catalyst unit weight used per unit time (h) kg / g Cat.hr, preferably 2.0 kg / g Cat.hr or higher, more preferably 3.0 kg / g Cat.hr or higher, or 4.7 kg / g Cat.hr or higher.

The stereoregularity (XI) of the polyolefin may be 90% or more, preferably 92% or more, more preferably 95% or more. At this time, the stereoregularity (XI) of the polyolefin is a value calculated according to the following expression (1).

[Equation 1]

The stereoregularity diagram (XI) = 100 - Xs

In the above equation 1,

Xs = fraction (wt%) of o -xylene in the polymer,

Vb0 = volume of initial o -xylene (mL),

Vb1 = volume (mL) of polymer dissolved in o -xylene,

Vb2 = volume (mL) of o-xylene collected during the blank test,

W2 = sum of polymer weight remaining in aluminum pan (g) after evaporation of aluminum pan and o -xylene,

W1 = weight of aluminum pan (g),

W0 = weight of initial polymer (g),

B = mean value (g) of the residue remaining in the aluminum pan during ball testing.

The polyolefin prepared through bulk polymerization according to the present invention can remarkably improve the polymer melting point (Tm) as well as the stereoregularity (XI) as described above. The melting point of the polyolefin may be at least 140 degrees or from 140 degrees to 180 degrees, preferably at least 143 degrees, more preferably at least 145 degrees.

In the present invention, matters other than those described above can be added or subtracted as required, and therefore, the present invention is not particularly limited thereto.

The catalyst for olefin polymerization according to the present invention can easily control the microstructure of the polymer and can achieve very excellent catalytic activity by supporting a novel anisometallocene compound and two kinds of promoter compounds.

In particular, the supported catalyst of the present invention exhibits improved activity in all cases even if the various supporting reaction conditions of the anisometallocene compound are changed. When the polyolefin is produced using the supported catalyst of the present invention, a highly active polyolefin polymer free of fouling can be easily produced.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example 1]

Under the conditions shown in the following Table 1, the anisometallocene compound of Formula 2 was prepared in the following manner, the above metallocene compound was carried on silica supported on methylaluminoxane, Supported catalyst to prepare a supported catalyst for olefin polymerization.

(3)

Preparation of metallocene compounds

Step 1: Preparation of (6-t-butoxyhexyl) dichloromethylsilane

100 mL of a solution of t-butoxyhexyl magnesium chloride (about 0.14 mol, ether) was added dropwise to 100 mL of a trichloromethylsilane solution (about 0.21 mol, hexane) at -100 ° C over 3 hours, And stirred for 3 hours.

After separating the transparent organic layer from the mixed solution, the separated transparent organic layer was vacuum dried to remove excess trichloromethylsilane. Thus, a transparent liquid (6-t-butoxyhexyl) dichloromethylsilane was obtained (yield: 84%).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.76 (3H, s), 1.11 (2H, t), 1.18 (9H, s), 1.32 ~ 1.55 (8H, m), 3.33 (2H, t)

Step 2: Preparation of (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-phenylindenyl) silane

15.4 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (34.9 mmol) The mixture was stirred for 1 hour and then at room temperature for one day. Subsequently, 5 g of the (6-t-butoxyhexyl) dichloromethylsilane prepared previously was slowly added dropwise to the mixed solution at -78 ° C, and the mixture was stirred for about 10 minutes and then at 80 ° C for 1 hour. Then, the organic layer was separated by adding water, and the silica column was purified and vacuum dried to obtain a sticky yellow oil in a yield of 78% (racemic: meso = 1: 1)

¹ H NMR (500 MHz, CDCl ₃ , 7.24 ppm): 0.10 (3H, s), 0.98 (2H, t), 1.25 (9H, s), 1.36-1.50 , 2.26 (6H, s), 3.34 (2H, t), 3.81 (2H, s), 6.87 7.53 (4 H, t), 7.61 (4 H, d)

Step 3: Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-phenylindenyl)] zirconium dichloride

To a solution of the above-prepared (6-t-butoxyhexyl) (methyl) bis (2-methyl-4-phenyl) indenylsilane ether / hexane = 1/1 solution (3.37 mmol) in n-butyl lithium M in hexane) was slowly added dropwise at -78 ° C, stirred at room temperature for about 2 hours, and then vacuum-dried. Then, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was weighed in a Schlenk flask, ether was slowly added dropwise at -78 ° C., And stirred for one day. Thereafter, the red reaction solution was separated by filtration, 4 equivalents of an HCl ether solution (1M) was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for 3 hours. Filtration and vacuum drying afforded the anthra-metallocene compound as an orange solid in 85% yield (racemic: meso = 10: 1).

^{1 H NMR (500 MHz, C} 6 D 6, 7.24 ppm): 1.19 (9H, s), 1.32 (3H, s), 1.48 ~ 1.86 (10H, m), 2.25 (6H, s), 3.37 (2H, d), 7.67 (2H, d), 7.63 (2H, d), 6.95

Preparation of Supported Catalyst

Silica XPO 2212, 3 g, was preliminarily weighed into a shrinking flask, and then 52 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 240 占 퐉 ol of the synthesized anthra-metallocene compound was dissolved in toluene and reacted at 48 占 폚 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. 240 ol ol of trityl tetrakis (pentafluorophenyl) borate was reacted at 77 캜 for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum-dried to obtain 5 g of silica-supported metallocene catalyst in the form of solid particles.

[Example 2]

Under the conditions shown in Table 1 below, the anthra-metallocene compound of Formula 3 was prepared as described above, and the metallocene compound was supported on the silica after supporting methylaluminoxane. Then, the boron- Supported catalyst to prepare an olefin polymerization supported catalyst.

Preparation of Supported Catalyst

Silica XPO 2410 (3 g) was preliminarily weighed into a shrinkage flask, and 40 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. After dissolving 360 μmol of the synthesized anthra-metallocene compound in toluene, the mixture was reacted at 75 ° C. for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. And 252 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate were reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Example 3]

Under the conditions shown in Table 1 below, the anthra-metallocene compound of Formula 3 was prepared as described above, and the metallocene compound was supported on the silica after supporting methylaluminoxane. Then, the boron- Supported catalyst to prepare an olefin polymerization supported catalyst.

Preparation of Supported Catalyst

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 40 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. After dissolving 360 μmol of the synthesized anthra-metallocene compound in toluene, the mixture was reacted at 75 ° C. for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. And 252 μmol of dimethylanilinium tetrakis (pentafluorophenyl) borate were reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Example 4]

Under the conditions shown in Table 1 below, the anthra-metallocene compound of Formula 3 was prepared as described above, and the metallocene compound was supported on the silica after supporting methylaluminoxane. Then, the boron- Supported catalyst to prepare an olefin polymerization supported catalyst.

Preparation of Supported Catalyst

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 40 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. The synthesized anthra-metallocene compound (480 μmol) was dissolved in toluene and reacted at 75 ° C. for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate (192 μmol) were reacted at 75 ° C. for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Example 5]

Under the conditions shown in Table 1 below, the anthra-metallocene compound of Formula 3 was prepared as described above, and the metallocene compound was supported on the silica after supporting methylaluminoxane. Then, the boron- Supported catalyst to prepare an olefin polymerization supported catalyst.

Preparation of Supported Catalyst

3 g of silica L203F was preliminarily weighed in a shrinking flask, and 40 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. The synthesized anthra-metallocene compound (480 μmol) was dissolved in toluene and reacted at 75 ° C. for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. 336 占 퐉 ol of dimethylanilinium tetrakis (pentafluorophenyl) borate was reacted at 75 占 폚 for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Example 6]

Under the conditions shown in Table 1 below, the anthra-metallocene compound of Formula 3 was prepared as described above, and the metallocene compound was supported on the silica after supporting methylaluminoxane. Then, the boron- Supported catalyst to prepare an olefin polymerization supported catalyst.

Preparation of Supported Catalyst

Silica XPO 2212, 3 g, was preliminarily weighed into a shrinking flask, and then 52 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 240 ol mol of the synthesized anthra-metallocene compound was dissolved in toluene and reacted at 40 캜 for 5 hours. After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate (240 μmol) was reacted at 70 ° C for 5 hours. After completion of the reaction, the reaction mixture was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Comparative Example 1]

A supported catalyst for olefin polymerization containing an anisometallocene compound was prepared in the same manner as in Example 1 except that only methyl aluminoxane was supported as a cocatalyst and no additional boron cocatalyst was used.

[Comparative Example 2]

A supported catalyst for olefin polymerization containing an anisometallocene compound was prepared in the same manner as in Example 2 except that only methyl aluminoxane was supported as a cocatalyst and no separate boron cocatalyst was used.

[Comparative Example 3]

A supported catalyst for olefin polymerization containing an anisometallocene compound was prepared in the same manner as in Example 3, except that only methyl aluminoxane was supported as a cocatalyst and no additional boron cocatalyst was used.

[Comparative Example 4]

A supported catalyst for olefin polymerization was prepared in the same manner as in Example 6, except that an anisate-metallocene compound represented by the following formula (4) was used.

In particular, an anisma-metallocene compound of Formula 4 and a catalyst for olefin polymerization comprising the same were prepared in the following manner.

[Chemical Formula 4]

Preparation of metallocene compounds

Step 1: Preparation of dimethyl bis (2-methyl-4-phenylindenyl) silane

21.8 mL of n-butyllithium solution (2.5 M, hexane solvent) was slowly added dropwise to 77 mL of 2-methyl-4-phenylindene toluene / THF = 10/1 solution (49.5 mmol) at 0 ° C, The mixture was stirred for 1 hour and then at room temperature for one day. Thereafter, 2.98 mL of dichloromethylsilane was slowly added dropwise at 0 DEG C or lower, stirred for about 10 minutes, then heated to 80 DEG C and stirred for 1 hour. The organic layer was separated by adding water, and the silica column was purified and vacuum dried to obtain a sticky yellow oil (yield: racemic: meso = 1: 1).

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.02 (6H, s), 2.37 (6H, s), 4.00 (2H, s), 6.87 (2H, t), 7.38 (2H, t), 7.45 (2H, t), 7.57 (4H, d), 7.65 (4H, t), 7.75

Step 2: Preparation of [dimethylsilanediylbis (2-methyl-4-phenylindenyl)] zirconium dichloride

10.9 mL of a n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 240 mL of a dimethyl bis (2-methyl-4-phenylindenyl) silane ether / hexane = 1/1 solution (12.4 mmol) Respectively. Thereafter, the mixture was stirred at room temperature for one day, filtered and vacuum dried to obtain a pale yellow solid. The ligand salt synthesized in a glove box and bis (N, N'-diphenyl-1,3-propanediamido) dichloro zirconium bis (tetrahydrofuran) were dissolved in a Schlenk flask ), Ether was slowly added dropwise at -78 ° C, and the mixture was stirred at room temperature for one day. The red solution was separated by filtration, dried in vacuo, and a toluene / ether = 1/2 solution was added to obtain a clear red solution. 1.5-2 equivalent of HCl ether solution (1M) was slowly added dropwise at -78 deg. C, followed by stirring at room temperature for 3 hours. After filtration and vacuum drying, the catalyst of orange solid component was obtained in a yield of 70% (racemic only).

^{1 H NMR (500 MHz, C} 6 D 6, 7.24 ppm): 1.32 (6H, s), 2.24 (6H, s), 6.93 (2H, s), 7.10 (2H, t), 7.32 (2H, t) , 7.36 (2H, d), 7.43 (4H, t), 7.60 (4H, d), 7.64

Preparation of Supported Catalyst

Silica XPO 2212, 3 g, was preliminarily weighed into a shrinking flask, and then 52 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. 240 [mu] mol of the anthra-metallocene compound of the formula 4 synthesized above, i.e., dimethylsilanediylbis (2-methyl-4-phenylindenyl)] zirconium dichloride was dissolved in toluene, Lt; / RTI > After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate (240 μmol) was reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

[Comparative Example 5]

A supported catalyst for olefin polymerization was prepared in the same manner as in Example 6 except that an anisate-metallocene compound represented by the following formula (5) was used.

In particular, an anisma-metallocene compound of Formula 5 and a catalyst for olefin polymerization comprising the same were prepared in the following manner.

[Chemical Formula 5]

Preparation of metallocene compounds

Step 1: Preparation of dimethyl bis (2-methyl-4,6-diisopropylindenyl) silane

7.83 mL of n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 10 mL of a solution of 2-methyl-4,6-isopropylindene (3.45 mmol in ether) at 0 ° C, The mixture was stirred at room temperature for about 3 hours. Thereafter, 0.2 mL of dichloromethylsilane was slowly added dropwise at 0 占 폚 or lower, and the mixture was stirred for about 10 minutes, and then the mixture was stirred at room temperature for 3 hours. The reaction product was then filtered and vacuum dried to give

^{1 H NMR (500 MHz, CDCl} 3, 7.24 ppm): 0.39 (6H, s), 1.30 ~ 1.23 (24H, m), 2.25 (6H, m), 2.91 (2H, q), 3.18 (2H, q) , 3.53 (2H, s), 6.71 (2H, s), 6.95 (2H, s), 7.14

Step 2: Preparation of [dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl)] zirconium dichloride

2.3 mL of a n-butyllithium solution (2.5 M in hexane) was slowly added dropwise to 10 mL of a dimethyl bis (2-methyl-4,6-diisopropylindenyl) silane solution (2.55 mmol in ether) , Stirred at room temperature for about 4 hours, and vacuum dried. Thereafter, the salt was washed with hexane, followed by filtration and vacuum drying to obtain a white solid. After dissolving it in toluene and dimethoxyethane, ZrCl ₄ toluene slurry was added thereto at -78 ° C, and the mixture was stirred at room temperature for about 3 hours. After drying in vacuo, hexane was added and the mixture was filtered at a low temperature to obtain [dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl)] zirconium dichloride (racemic: meso = 1: 1).

^{1 H NMR (500 MHz, C} 6 D 6, 7.24 ppm): 1.19 ~ 1.34 (30H, m), 2.22 (6H, s), 2.84 (2H, q), 3.03 (2H, q), 6.79 (2H, s), 7.04 (2H, q), 7.27 (2H, s)

Preparation of Supported Catalyst

Silica XPO 2212, 3 g, was preliminarily weighed into a shrinking flask, and then 52 mmol of methylaluminoxane (MAO) was added thereto, followed by reaction at 95 ° C for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene. After dissolving 240 μmol of the anthra-metallocene compound of the formula 5 synthesized above, ie, dimethylsilanediylbis (2-methyl-4-phenylindenyl)] zirconium dichloride in toluene, Lt; / RTI > After the completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed with toluene. Dimethylanilinium tetrakis (pentafluorophenyl) borate (240 μmol) was reacted at 75 ° C for 5 hours. After completion of the reaction, the reaction product was washed with toluene, washed again with hexane, and vacuum dried to obtain a silica-supported metallocene catalyst in the form of solid particles.

carrier
Kinds MAO
content
(mmol) MAO
Supported reaction temperature
(° C) MAO Carrying
Reaction time
(hr) Metallocene catalyst content
(umol) Catalyst supporting reaction temperature
(° C) Catalyst supporting reaction time
(hr) Borre
It
content
(umol) Borate / catalyst
Mole ratio Borate supported reaction temperature
(° C) Borate supported reaction time
(hr) Example
One XPO 2212 52 95 24 240 48 5 TB
240 One 77 5 Example
2 XPO 2410 40 95 24 360 75 5 AB
252 0.7 75 5 Example
3 L203F 40 95 24 360 75 5 AB
252 0.7 75 5 Example
4 L203F 40 95 24 480 75 5 AB
192 0.4 75 5 Example
5 L203F 40 95 24 480 75 5 AB
336 0.7 75 5 Example
6 XPO 2212 52 95 24 240 40 5 AB
240 One 70 5 Comparative Example
One XPO 2212 52 95 24 240 48 5 - - - - Comparative Example
2 XPO 2410 40 95 24 360 75 5 - - - - Comparative Example
3 L203F 30 95 24 240 75 5 - - - - Comparative Example
4 XPO
2212 52 95 24 240 40 5 AB
240 One 75 5 Comparative Example
5 XPO
2212 52 95 24 240 40 5 AB
240 One 75 5 TB: trityl tetrakis (pentafluorophenyl) borate, [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ]
AB: Dimethylanilinium tetrakis (pentafluorophenyl) borate, [HNMe ₂ Ph] [B (C ₆ F ₅ ) ₄ ]
The molar ratio of the borate / catalyst to the boron-based promoter molar ratio

[Production Examples 1 to 6 and Comparative Production Examples 1 to 5]

Polypropylene (PP) polymers were prepared in the following manner using the metallocene supported catalysts prepared in Examples 1 to 6 and Comparative Examples 1 to 5, respectively.

Propylene polymerization

First, a 2 L stainless steel reactor was vacuum dried at 65 deg. C and then cooled. 1.5 mmol of triethylaluminum was added at room temperature, 0.37 L of hydrogen was added, and 1.5 L of propylene was added sequentially. After stirring for 10 minutes, the supported metallocene catalysts prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were introduced into the reactor under nitrogen pressure. Thereafter, the temperature of the reactor was elevated to 70 ° C within 5 minutes and then polymerized for 1 hour. After the completion of the reaction, unreacted propylene was bubbled.

At this time, the mass of the anammetallocene compound, the supported catalyst mass, the mass (kg) of the produced polypropylene, and the activity were measured and shown in Table 2 below.

≪ Measurement method of physical properties of polymer &

Catalytic activity: The ratio of the weight of the polymer produced per gram of supported catalyst mass (kg PP) to the weight of metallocene compound (umol) contained in the supported catalyst based on the unit time (h) Weight (kg PP).

The polymerization process conditions of Production Examples 1 to 6 and Comparative Production Examples 1 to 5 using the metallocene supported catalysts prepared through Examples 1 to 6 and Comparative Examples 1 to 5 and the measurement results of activity of the produced polypropylene are shown in the following Table As shown in Fig.

Catalyst type Liquid
Pro
Filen
(L) Amount of catalyst
(μmol) Bearing
Amount of catalyst
(g) polymerization
Way polymerization
Temperature
(° C) Hydrogen
(L) The polymer (g) activation
(kg /
mmol · hr) activation
(kg /
gCat 占 hr) Production Example 1 Example
One 1.5 1.96 0.052 bulk
polymerization 70 0.37 271 138.5 5.21 Production Example 2 Example
2 1.5 3.72 0.06 bulk
polymerization 70 0.37 430 115.7 7.17 Production Example 3 Example
3 1.5 3.64 0.059 bulk
polymerization 70 0.37 401 110 6.8 Production Example 4 Example
4 1.5 2.58 0.031 bulk
polymerization 70 0.37 381 147.9 12.2 Production Example 5 Example
5 1.5 2.5 0.03 bulk
polymerization 70 0.37 416 166.7 13.9 Production Example 6 Example
6 1.5 2.3 0.061 bulk
polymerization 70 0.37 402 175.1 6.59 compare
Manufacturing example
One Comparative Example
One 1.5 2.14 0.055 bulk
polymerization 70 0.37 194 90.7 3.53 compare
Manufacturing example
2 Comparative Example
2 1.5 3.72 0.058 bulk
polymerization 70 0.37 269 72.2 4.63 compare
Production Example 3 Comparative Example
3 1.5 2.76 0.060 bulk
polymerization 70 0.37 137 49.7 2.30 compare
Manufacturing example
4 Comparative Example
4 1.5 5.50 0.146 bulk
polymerization 70 0.37 80 14.6 0.55 compare
Manufacturing example
5 Comparative Example
5 1.5 5.50 0.146 bulk
polymerization 70 0.37 - - -

As shown in Table 2 above, it was confirmed that the support of Examples 1 to 6, which was prepared by using the novel anisometalloc metallocene compound according to the present invention with a specific promoter, that is, using the alkylaluminoxane and the boron- Metallocene compounds were used as catalysts or polypropylene polymerization was carried out using catalysts or catalysts of comparative examples 1 to 5 which were prepared by conventional methods using conventional catalysts Able to know. Particularly, the catalytic activity was far superior to that of Comparative Production Example 4 and Comparative Production Example 5 using two kinds of promoters, and in Comparative Production Example 5, no polypropylene polymerization occurred.

On the other hand, Examples 2 to 3 and 5, wherein the molar ratio of the boron-containing promoter to the anhydro metallocene compound is 0.7, show better catalytic activity. In addition, it can be seen that activity increases more in Production Examples 2 to 6 using dimethylanilinium tetrakis (pentafluorophenyl) borate (AB) as a boron-based promoter.

As a result, it can be seen that the supported catalyst of the present invention has a higher activity than that of a metallocene supported catalyst which is supported on a common alkylaromatic acid. This can be attributed to the fact that a two-component catalyst, particularly an alkyl aluminoxane-based co-catalyst, and a boron-based co-catalyst were supported. By doing so, the catalyst for olefin polymerization of the present invention can exhibit improved activity irrespective of the state of silica, the amount of supported metallocene compound, and the temperature and time during the supporting reaction.

Claims (8)

An olefin polymerization catalyst supported with an anhydride-metallocene compound represented by the following general formula (1), an alkylaluminoxane-based promoter, and a boron-based promoter:
[Chemical Formula 1]

In Formula 1,
M ¹ is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide series transition metal or an ethanide series transition metal;
X is the same or different halogen;
A is a bridge group connecting an indenyl group as an element of Group 14;
R ¹ is alkyl having 1 to 4 carbon atoms;
R ² is hydrogen or alkyl having 1 to 4 carbon atoms;
R ³ and R ^{3 '} are the same or different from each other and each is alkyl having 1 to 6 carbon atoms;
R ⁴ and R ^{4 '} are the same or different and each is aryl having 6 to 20 carbon atoms;
n is an integer of 1 to 6; The method according to claim 1,
Wherein the anisometallocene compound is represented by the following general formula (3).
(3)

The method according to claim 1,
Wherein the alkylaluminoxane-based co-catalyst is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, propyl aluminoxane, and butyl aluminoxane. The method according to claim 1,
Wherein the boron-based promoter is selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, and methylanilinium tetrakis (pentafluorodiphenyl) At least one olefin polymerization catalyst selected from the group consisting of: The method according to claim 1,
Wherein the catalyst is supported on at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia. A process for producing a polyolefin comprising polymerizing at least one olefin monomer in the presence of the catalyst according to any one of claims 1 to 5. The method according to claim 6,
Wherein the polymerization of the polyolefin is carried out by reacting for 1 to 24 hours at a temperature of 25 to 500 DEG C and a pressure of 1 to 100 kgf / cm < ² >. The method according to claim 6,
The olefin monomer may be selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, , 1-octadecene, 1-eicosene, and mixtures thereof.