Supported hybrid metallocene catalyst, and method for preparing polyolefin using the same

Abstract

The present disclosure relates to a supported hybrid metallocene catalyst and a method for preparing a polyolefin using the same. When the supported hybrid metallocene catalyst according to the present disclosure is used, a polyolefin with a multimodal molecular weight distribution and excellent environmental stress crack resistance can be prepared.

Claims

1. A supported hybrid metallocene catalyst, comprising: a first metallocene compound represented by the following Chemical Formula 1; a second metallocene compound which is represented by the following Chemical Formula 2 and one of C.sub.1 and C.sub.2 of Chemical Formula 2 is represented by the following Chemical Formula 3a; a third metallocene compound which is represented by the following Chemical Formula 2 and one of C.sub.1 and C.sub.2 of Chemical Formula 2 is represented by the following Chemical Formula 3b; a cocatalyst; and a support: ##STR00012## in Chemical Formula 1, at least one of R.sub.1 to R.sub.8 is (CH.sub.2).sub.nOR, wherein R is a C1 to C6 linear or branched alkyl group, and n is an integer of 2 to 10, and the others are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, M.sub.1 is a Group 4 transition metal, and X.sub.1 and X.sub.2 are the same as or different from each other, and are each independently a halogen or a C1 to C20 alkyl group, ##STR00013## in Chemical Formula 2, M.sub.2 is a Group 4 transition metal, X.sub.3 and X.sub.4 are the same as or different from each other, and are each independently a halogen or a C1 to C20 alkyl group, B is carbon, silicon, or germanium, at least one of Q.sub.1 and Q.sub.2 is (CH.sub.2).sub.mOR, wherein R is a C1 to C6 linear or branched alkyl group, and m is an integer of 2 to 10, and the others are the same as or different from each other, and are each independently hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, and one of C.sub.1 and C.sub.2 is represented by the following Chemical Formula 3a or 3b, and the other is represented by the following Chemical Formula 3c, ##STR00014## in Chemical Formulae 3a to 3c, R.sub.9 to R.sub.27 are the same as or different from each other, and are each independently hydrogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

2. The supported hybrid metallocene catalyst of claim 1, wherein at least one of R.sub.1 and R.sub.5 of Chemical Formula 1 is (CH.sub.2).sub.nOR, wherein R is a C1 to C6 linear or branched alkyl group, and n is an integer of 2 to 10.

3. The supported hybrid metallocene catalyst of claim 1, wherein R.sub.10 of Chemical Formula 3a is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

4. The supported hybrid metallocene catalyst of claim 1, wherein at least one of R.sub.24 and R.sub.27 of Chemical Formula 3c is a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkoxy group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group.

5. The supported hybrid metallocene catalyst of claim 1, wherein the first metallocene compound is selected from the group consisting of the following structural formulae: ##STR00015##

6. The supported hybrid metallocene catalyst of claim 1, wherein the second metallocene compound is selected from the group consisting of the following structural formulae: ##STR00016##

7. The supported hybrid metallocene catalyst of claim 1, wherein the third metallocene compound is represented by the following structural formula: ##STR00017##

8. The supported hybrid metallocene catalyst of claim 1, wherein a molar mixing ratio of the first metallocene compound to the second metallocene compound to the third metallocene compound is 1:0.1 to 5:0.1 to 5.

9. The supported hybrid metallocene catalyst of claim 1, wherein the cocatalyst comprises at least one selected from the group consisting of a first cocatalyst represented by the following Chemical Formula 4 and a second cocatalyst represented by the following Chemical Formula 5:
[Al(R.sub.28)O].sub.k[CHEMICAL FORMULA 4] in Chemical Formula 4, each R.sub.28 is the same as or different from each other, and each is independently a halogen, or a C1 to C20 hydrocarbyl group substituted or unsubstituted with a halogen, and k is an integer of 2 or more,
T.sup.+[BG.sub.4].sup.[CHEMICAL FORMULA 5] in Chemical Formula 5, T.sup.+ is a polyatomic ion having a valence of +1, B is boron in a +3 oxidation state, and each G is independently selected from the group consisting of hydride, dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, halocarbyl, and halo-substituted hydrocarbyl, and G has 20 or fewer carbons, provided that G is a halide in one or fewer positions.

10. A method for preparing a polyolefin, comprising the step of polymerizing olefinic monomers in the presence of the supported hybrid metallocene catalyst of claim 1.

11. The method of claim 10, wherein the olefinic monomers include at least one selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, and 3-chloromethylstyrene.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The present invention will be described in more detail with reference to the following examples. However, these examples are for illustrative purposes only, and the invention is not intended to be limited by these examples.

Preparation Example 1: Preparation of the First Metallocene Compound

(2) ##STR00009##

(3) 1-1 Preparation of Ligand Compound

(4) 10.8 g (100 mmol) of chlorobutanol was placed into a dried 250 mL Schlenk flask, 10 g of a molecular sieve and 100 mL of MTBE were added thereto, and then 20 g of sulfuric acid was slowly added thereto over 30 minutes. The reaction mixture slowly turned pink with time. After 16 hours, it was poured into a saturated sodium bicarbonate solution which was cooled down using ice. The mixture was extracted with ether (100 mL4) several times. After the extracted organic layers were dried using MgSO.sub.4 and filtered, the solvent was removed under vacuum-reduced pressure to obtain 10 g of a yellow liquid, 1-(tert butoxy)-4-chlorobutane (60% yield).

(5) .sup.1H NMR (500 MHz, CDCl.sub.3): 1.16 (9H, s), 1.671.76 (2H, m), 1.861.90 (2H, m), 1.94 (1H, m), 3.36 (2H, m), 3.44 (1H, m), 3.57 (3H, m)

(6) 4.5 g (25 mmol) of synthesized 1-(tert butoxy)-4-chlorobutane was added into a dried 250 mL Schlenk flask, and dissolved in 40 mL of THF. 20 mL of a sodium cyclopentadienylide THF solution was slowly added thereto and stirred for one day. The reaction mixture was quenched by adding 50 mL of water, extracted with ether (50 mL3), and then the extracted organic layers were washed with brine. After the remaining water was dried using MgSO.sub.4 and filtered, the solvent was removed under vacuum-reduced pressure to obtain a dark brown viscous product, 2-(4-(tert-butoxy)butyl) cyclopenta-1,3-diene in a quantitative yield.

(7) .sup.1H NMR (500 MHz, CDCl.sub.3): 1.16 (9H, s), 1.541.60 (4H, m), 1.65 (1H, m), 1.82 (1H, m), 2.372.42 (2H, m), 2.87, 2.92 (2H, s), 3.36 (2H, m), 5.99 (0.5H, s), 6.17 (0.5H, s), 6.25 (0.5H, s), 6.34 (0.5H, s), 6.42 (1H, s)

(8) 1-2 Preparation of Metallocene Compound

(9) 4.3 g (23 mmol) of the ligand compound synthesized in 1-1 was placed into a dried 250 mL Schlenk flask and dissolved in 60 mL of THF. 11 mL of an n-BuLi 2.0 M hexane solution (28 mmol) was added thereto, and stirred for one day. Then, this solution was added into a flask at 78 C. in which 3.83 g (10.3 mmol) of ZrCl.sub.4(THF).sub.2 was dispersed in 50 mL of ether.

(10) When the reaction mixture was heated to room temperature, a light brown suspension turned into a pale yellow suspension. After stirring for one day, all of the solvent of the reaction mixture was dried, and 200 mL of hexane was added thereto for sonication. Then, the hexane solution on the upper layer was collected by decantation with a cannula. The hexane solution obtained by repeating this process twice was dried under vacuum-reduced pressure to obtain a pale yellow solid product, bis(3-(4-(tert-butoxy)butyl-2,4-dien-yl) zirconium(IV) chloride.

(11) .sup.1H NMR (500 MHz, CDCl.sub.3): 0.84 (6H, m), 1.14 (18H, s), 1.551.61 (8H, m), 2.61 (4H, m), 3.38 (4H, m), 6.22 (3H, s), 6.28 (3H, s)

Preparation Example 2: Preparation of the Second Metallocene Compound

(12) ##STR00010##

(13) 2-1 Preparation of Ligand Compound

(14) 1.7 g (10 mmol) of 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole was placed into a dried 250 mL Schlenk flask and 40 mL of ether was injected under argon. After cooling the ether solution to 0 C., 4.8 mL (12 mmol) of a 2.5 M n-BuLi hexane solution was slowly added dropwise. The reaction mixture was slowly heated to room temperature and stirred until the next day. After 20 mL of ether was placed in another 250 mL Schlenk flask, 3.6 mL (30 mmol) of dichloromethyl(tertbutoxyhexyl)silane was added thereto. After cooling the flask to 78 C., a lithiated solution of indenoindole was injected through a cannula. After the injection was completed, the reaction mixture was slowly heated to room temperature, stirred for about 5 hours, and then stirred for one day. After quenching by adding 50 mL of water, the organic layers were extracted, and dried using MgSO.sub.4. The ether used as the solvent was removed under reduced pressure. It was confirmed by NMR that 10-((6-(tert-butoxy)hexyl)chloro(methyl)silyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole was obtained with a yield of about 95% or more.

(15) After the synthesis of the indenoindole part was confirmed, 1.7 g (10 mmol) of 3-(but-3-en-1-yl)-1H-indene was placed in a dried 100 mL Schlenk flask and dissolved in 40 mL of ether. Then, 4.8 ml (12 mmol) of a 2.5 M n-BuLi hexane solution was slowly added dropwise at 78 C. and stirred for one day. 10-((6-(tert-butoxy)hexyl)chloro(methyl)silyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole prepared above was dissolved in 40 mL of ether, and then a lithiated solution of buthylindene was added dropwise at 78 C. After about 20 hours, it was quenched by adding 50 mL of water to extract the organic layers, followed by drying using MgSO.sub.4. The solvent of the mixture obtained by filtration was evaporated under vacuum-reduced pressure. Therefore, 5.8 g (9.7 mmol, 97.1%) of 10-((3-(but-3-en-1-yl)-1H-inden-1-yl)(6-(tert-butoxy)hexyl)(methyl)silyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole was obtained.

(16) .sup.1H NMR (500 MHz, CDCl3): 0.71, 0.23 (3H, d), 0.82 (2H, s), 1.17 (9H, s), 1.23 1.39 (7H, m), 1.51 (1H, s), 2.26 (2H, m), 2.48 (2H, m), 2.61 (2H, m), 3.25 (2H, m), 3.50 (1H, s), 3.82 (1H, s), 4.09 (3H, m), 5.03 (2H, m), 5.89 (1H, m), 7.08 (1H, s), 7.157.75 (11H, m)

(17) 2-2 Preparation of Metallocene Compound

(18) The ligand was placed in a 250 mL oven-dried Schlenk flask, and dissolved in ether. 2.1 equivalents of an n-BuLi solution was added thereto and lithiated until the next day. In a glove box, one equivalent of ZrCl.sub.4(THF).sub.2 was taken and placed in a 250 ml Schlenk flask to prepare a suspension containing ether or toluene. Both flasks were cooled down to 78 C. and ligand anions were slowly added to the Zr suspension. After the injection, the reaction mixture was slowly heated to room temperature. It was confirmed that, when the metallization was successfully carried out in this process, a purple color peculiar to the catalyst precursor appeared. After stirring it for one day, the toluene or ether in the mixture was removed under vacuum-reduced pressure to about volume, and hexane was added thereto in a volume of about 5 times that of the remaining solvent. The reason for adding hexane at this time is to promote crystallization, because the synthesized catalyst precursor has low solubility in hexane. The hexane slurry was filtered under argon, and both the filtered solid and the filtrate were evaporated under vacuum-reduced pressure. The remaining filter cake was weighed and sampled in the glove box to confirm the synthesis, yield, and purity. Ether was used as a solvent in the metallation, and 2.5 g (30.5%) of a purple solid was obtained from 5.8 g (9.7 mmol) of ligand (purity (wt %)=90% by NMR, Mw=762.06).

(19) .sup.1H NMR (500 MHz, CDCl.sub.3): 0.81 (3H, m), 1.19 (10H, m), 1.551.78 (10H, m), 1.97 (2H, m), 2.26 (2H, m), 2.54 (3H, s), 3.36 (2H, m), 3.94 (3H, s), 4.16 (1H, d), 4.85 (1H, m), 5.64 (1H, s), 6.53 (1H, s), 6.97 (2H, m), 7.107.45 (5H, m), 7.527.87 (4H, m)

Preparation Example 3: Preparation of the Third Metallocene Compound

(20) ##STR00011##

(21) 3-1 Preparation of Ligand Compound

(22) 3 g (10 mmol) of an indenoindole derivative was dissolved in 100 mL of hexane, and 4.4 mL (11 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise thereto, followed by stirring overnight at room temperature. Another 250 mL Schlenk flask was prepared and placed in a glove box. Then, 2.7 g (10 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was weighed and taken out of the glove box, dissolved in 50 mL of hexane, and then lithiated slurry was added dropwise thereto. The mixture was slowly heated to room temperature and stirred overnight. 10 mmol of sodium Cp salt was dissolved in 100 mL of THF, and then added dropwise to the mixture, followed by stirring overnight at room temperature. After the reaction, the residual moisture in organic layers was removed by extraction with MgSO.sub.4, and the solvent was removed under vacuum-reduced pressure to obtain a ligand compound in an oily state. This was confirmed by .sup.1H NMR.

(23) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.746.49 (7H, m), 5.87 (6H, s), 3.32 (2H, m), 3.49 (3H, s), 1.501.25 (8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17 (3H, d)

(24) 3-2 Preparation of Metallocene Compound

(25) 7.9 mmol of the ligand compound synthesized in 3-1 was dissolved in 80 mL of toluene, and 6.6 mL (16.6 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise thereto, followed by stirring overnight at room temperature. 7.9 mmol of ZrCl.sub.4(THF).sub.2 was prepared as a slurry in 80 mL of toluene, and the ligand-Li solution was transferred thereto and stirred.

(26) The reaction mixture was filtered to remove LiCl, and toluene of the filtrate was vacuum dried to obtain 1.5 g of a liquid catalyst with a yield of 23 mol %.

(27) .sup.1H NMR (500 MHz, CDCl.sub.3): 7.667.20 (17H, m), .sup.1H NMR (500 MHz, CDCl.sub.3): 7.896.53 (19H, m), 5.82 (4H, s), 3.19 (2H, s), 2.40 (3H, m), 1.351.21 (4H, m), 1.14 (9H, s), 0.970.9 (4H, m), 0.34 (3H, t)

Examples of Preparation of Supported Hybrid Metallocene Catalyst

Example 1

(28) 3 kg of a toluene solution was placed in a 20 L SUS reactor, and the reactor temperature was maintained at 40 C. 1 kg of silica (Sylopol 948, manufactured by Grace Davison), dehydrated by applying vacuum at 600 C. for 12 hours, was added into the reactor and sufficiently dispersed. Then, 3 kg of a 10 wt % methylaluminoxane (MAO)/toluene solution was added thereto, followed by stirring at 40 C. and 200 rpm for 12 hours.

(29) The metallocene compound of Preparation Example 3 was dissolved in toluene, and then added to the reactor at a ratio of 0.1 mmol/gSiO.sub.2, followed by stirring and reacting at 40 C. for 2 hours.

(30) Subsequently, the metallocene compound of Preparation Example 2 was added to the reactor at a ratio of 0.15 mmol/gSiO.sub.2, and then stirred at 40 C. and 200 rpm for 2 hours. The metallocene compound of Preparation Example 1 was added to the reactor at a ratio of 0.15 mmol/gSiO.sub.2, and then stirred at 40 C. and 200 rpm for 2 hours.

(31) The hexane slurry was transferred to a filter and the hexane solution was filtered. Subsequently, it was dried under reduced pressure at 40 C. for 4 hours to prepare 1 kg of a supported hybrid catalyst

Example 2

(32) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compound prepared in Preparation Example 1 was added at a ratio of 0.1 mmol/gSiO.sub.2.

Example 3

(33) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compound prepared in Preparation Example 1 was added at a ratio of 0.1 mmol/gSiO.sub.2, and the metallocene compound prepared in Preparation Example 2 was added at a ratio of 0.1 mmol/gSiO.sub.2.

Comparative Example 1

(34) A polyethylene copolymer (ME1000, manufactured by LG Chem Ltd.) prepared by using a Ziegler-Natta catalyst was used as Comparative Example 1.

Comparative Example 2

(35) A supported hybrid metallocene catalyst was prepared in the same manner as in Example 1, except that the metallocene compound prepared in Preparation Example 1 was added at a ratio of 0.1 mmol/gSiO.sub.2, the metallocene compound prepared in Preparation Example 2 was added at a ratio of 0.2 mmol/gSiO.sub.2, and the metallocene compound prepared in Preparation Example 3 was not added.

Experimental Example: Preparation of Ethylene/1-Butene Copolymer

(36) Each of the supported hybrid metallocene catalysts prepared in the examples was added into a CSTR continuous polymerization reactor (reactor volume of 50 L) to prepare an olefin polymer. 1-butene was used as a comonomer, and the reactor pressure was maintained at 10 bar and the polymerization temperature was maintained at 90 C.

(37) The polymerization conditions using the supported hybrid metallocene catalysts of Examples 1 to 3 and Comparative Examples 1 and 2 are summarized in Table 1 below.

(38) TABLE-US-00001 TABLE 1 Polymerization conditions Pressure (bar)/ Hydrogen 1-butene Catalyst Temp ( C.) (g/h) (cc/min) Example 1 Prep. Example 3 10/90 2.0 6 0.10 mmol/gSiO.sub.2 Prep. Example 2 0.15 mmol/gSiO.sub.2 Prep. Example 1 0.15 mmol/gSiO.sub.2 Example 2 Prep. Example 3 10/90 3.0 7 0.10 mmol/gSiO.sub.2 Prep. Example 2 0.15 mmol/gSiO.sub.2 Prep. Example 1 0.10 mmol/gSiO.sub.2 Example 3 Prep. Example 3 10/90 3.4 8 0.10 mmol/gSiO.sub.2 Prep. Example 2 0.10 mmol/gSiO.sub.2 Prep. Example 1 0.10 mmol/gSiO.sub.2 Comp. Example 1 10/90 2.0 4 Comp. Prep. Example 2 10/90 1.8 4 Example 2 0.20 mmol/gSiO.sub.2 Prep. Example 1 0.10 mmol/gSiO.sub.2

(39) The physical properties of the polyolefins prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following methods and are shown in Table 2.

(40) (1) Mn, Mw, PDI, GPC curve: The sample was pretreated by dissolving in 1,2,4-trichlorobenzene containing 0.0125% of BHT at 160 C. for 10 hours using PL-SP260. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured at 160 C. using PL-GPC220. PDI is represented by the ratio (Mw/Mn) between the weight average molecular weight and the number average molecular weight. In addition, the ratio of an integral value in the region of log Mw of 4.55.0, 5.05.5, or 5.56.0 to an integral value of the entire x-axis in a GPC curve graph having an x-axis of log Mw and a y-axis of dw/dlogMw was calculated and is shown in Table 2 below.

(41) (32) Density (g/cm.sup.3): It was measured according to ASTM 1505.

(42) (3) Melt index (MI, 2.16 kg): It was measured at 190 C. according to ASTM 1238.

(43) (4) ESCR: The number of hours to F50 (50% crack) was measured using a 10% Igepal CO-630 solution according to ASTM D 1693 at 50 C.

(44) (5) Spiral flow length: ENGEL 150 ton injection machine was used. The mold thickness was 1.5 mm, the injection temperature was 190 C., the mold temperature was 50 C., and the injection pressure was 90 bar.

(45) TABLE-US-00002 TABLE 2 Ex. 1 Ex. 2 Ex. 3 Comp. Ex. 1 Comp. Ex. 2 Catalytic activity (kgPE/gSiO.sub.2) 41.5 32.1 36.4 15.3 33.5 Mw (g/mol) 167,000 174,000 161,000 137,000 138,000 PDI 11.2 14.0 15.7 10.3 9.8 ESCR (h) 180 160 220 120 50 MI.sub.2 (g/10 min) 0.31 0.30 0.46 0.78 0.41 Density 0.951 0.951 0.953 0.952 0.952 Spiral Flow (cm) 16.1 15.3 17.3 10.0 10.0 Fraction (%) 4.5~5.0 22.91 19.51 18.31 26.77 20.4 5.0~5.5 14.55 13.50 10.46 21.15 21.9 5.5~6.0 10.39 9.92 8.76 9.85 8.40

(46) As shown in Table 2, the ethylene/alpha-olefin copolymer of Examples exhibits a broad molecular weight distribution, and its ratio in the region of log Mw of 5.0 to 5.5 satisfies a specific range. Therefore, it has the environmental stress crack resistance of 150 hours or more and the relatively high spiral flow length, indicating excellent processability and remarkably improved environmental stress crack resistance.