Ethylene/1-hexene copolymer having excellent processability and mechanical properties

Abstract

The ethylene/1-hexene copolymer according to the present invention has excellent processability and mechanical properties, and thus can be applied to various fields such as food containers.

Claims

1. An ethylene/1-hexene copolymer having the following features: a weight average molecular weight is 90,000 to 300,000; a density (g/cm.sup.3) is 0.950 to 0.965; a molecular weight distribution is 5 to 20; a MFR.sub.2.16 measured by ASTM 1238 under a load of 2.16 kg at 190 C. is 0.01 to 0.3 g/10 min; a melt flow rate ratio of MFR.sub.21.6/MFR.sub.5, measured by ASTM 1238 at 190 C., is 3 to 10; and a spiral flow length (cm) is 15 to 20, wherein the spiral flow length is evaluated by injecting the copolymer by applying a specific injection pressure and injection temperature to a spiral mold, and determining how much the molten and injected copolymer is pushed out, wherein the spiral mold has a thickness of 1.5 mm, the injection temperature is 190 C. a mold temperature is 50 C., and the injection pressure is 90 bar.

2. The ethylene/1-hexene copolymer of claim 1, wherein the molecular weight distribution is 10 to 15.

3. The ethylene/1-hexene copolymer of claim 1, wherein the melt flow rate ratio is 4 to 8.

4. The ethylene/1-hexene copolymer of claim 1, wherein the ethylene/1-hexene copolymer is prepared by copolymerizing ethylene and 1-hexene in the presence of a catalyst composition comprising a compound represented by the following Chemical Formula 1: ##STR00016## in Chemical Formula 1, M.sup.1 is a Group 4 transition metal; X.sup.1 is each independently halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, nitro, amido, C.sub.1-20 alkylsilyl, C.sub.1-20 alkoxy, or C.sub.1-20 sulfonate; n1 and m1 are each independently an integer of 1 to 4; and R.sup.11 and R.sup.12 are each independently hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl; with the proviso that at least one of R.sup.11 is C.sub.2-20 alkoxyalkyl.

5. The ethylene/1-hexene copolymer of claim 4, wherein the catalyst composition further comprises one or more of compounds represented by the following Chemical Formulas 2 to 4: ##STR00017## in Chemical Formula 2, M.sup.2 is a Group 4 transition metal; X.sup.2 is each independently halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, nitro, amido, C.sub.1-20 alkylsilyl, C.sub.1-20 alkoxy, or C.sub.1-20 sulfonate; L.sup.2 is C.sub.1-10 alkylene; n2 and m2 are each independently an integer of 1 to 4; and R.sup.21 and R.sup.22 are each independently hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl, ##STR00018## in Chemical Formula 3, M.sup.3 is a Group 4 transition metal; X.sup.3 is each independently halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, nitro, amido, C.sub.1-20 alkylsilyl, C.sub.1-20 alkoxy, or C.sub.1-20 sulfonate; L.sup.3 is Si(R.sup.34)(R.sup.35), wherein R.sup.34 and R.sup.35 are each independently C.sub.1-20 alkyl, or C.sub.1-10 alkoxy; n3 and m3 are each independently an integer of 1 to 4; and R.sup.31 and R.sup.32 are each independently hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 to aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl, ##STR00019## in Chemical Formula 4, M.sup.4 is a Group 4 transition metal; X.sup.4 is each independently halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, nitro, amido, C.sub.1-20 alkylsilyl, C.sub.1-10 alkoxy, or C.sub.1-20 sulfonate; L.sup.4 is Si(R.sup.44)(R.sup.45), wherein R.sup.44 and R.sup.45 are each independently C.sub.1-20 alkyl, or C.sub.1-10 alkoxy, with the proviso that at least one of R.sup.44 and R.sup.45 is 6-(tert-butoxy)hexyl; n4 and m4 are each independently an integer of 1 to 4; and R.sup.41 and R.sup.42 are each independently hydrogen, C.sub.1-20 alkyl, C.sub.1-10 alkoxy, C.sub.2-20 alkoxyalkyl, C.sub.6-20 aryl, C.sub.6-10 aryloxy, C.sub.2-20 alkenyl, C.sub.7-40 alkylaryl, C.sub.7-40 arylalkyl, C.sub.8-40 arylalkenyl, or C.sub.2-10 alkynyl.

6. The ethylene/1-hexene copolymer of claim 4, wherein the catalyst composition further comprise a compound represented by the following Chemical Formula 5: ##STR00020## in Chemical Formula 5, M.sup.5 is a Group 4 transition metal; X.sup.5 are each independently halogen, C.sub.1-20 alkyl, C.sub.2-20 alkenyl, C.sub.6-20 aryl, nitro, amido, C.sub.1-20 alkylsilyl, C.sub.1-20 alkoxy, or C.sub.1-20 sulfonate; L.sup.5 is C.sub.1-10 alkylene; and R.sup.5 is C.sub.1-10 alkoxy.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Hereinafter, preferred examples of the present invention will be described for the purpose of facilitating understanding of the present invention. However, these examples are given for illustrative purposes only and the scope of the present invention is not limited by the examples.

Preparation Example 1: Preparation of Precursor A

(2) ##STR00011##

(3) t-Butyl-O(CH.sub.2).sub.6Cl was prepared by using 6-chlorohexanol according to the method described in Tetrahedron Lett. 2951 (1988), and NaCp was reacted therewith to obtain t-Butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 (60% yield, b.p. 80 C./0.1 mmHg). Further, t-Butyl-O(CH.sub.2).sub.6C.sub.5H.sub.5 was dissolved in THF at 78 C., normal butyl lithium (n-BuLi) was slowly added thereto, warmed up to room temperature and then allowed to react for 8 hours. The previously synthesized lithium salt solution was slowly added again to a suspension solution of ZrCl.sub.4(THF).sub.2 (1.70 g, 4.50 mmol)/THF (30 mL) at 78 C., and further reacted at room temperature for 6 hours. All volatile materials were dried under vacuum, a hexane solvent was added to the obtained oily liquid material and filtered. The filtered solution was dried under vacuum, and hexane was then added thereto to induce precipitation at a low temperature (20 C.). The obtained precipitates were filtered at a low temperature to obtain a compound [tBu-O(CH.sub.2).sub.6C.sub.5H.sub.4].sub.2ZrCl.sub.2 in the form of a white solid (92% yield).

(4) .sup.1H NMR (300 MHz, CDCl3): 6.28 (t, J=2.6 Hz, 2H), 6.19 (t, J=2.6 Hz, 2H), 3.31 (t, 6.6 Hz, 2H), 2.62 (t, J=8 Hz), 1.7-1.3 (m, 8H), 1.17 (s, 9H).

(5) .sup.13C NMR (CDCl3): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.

Preparation Example 2: Preparation of Precursor B

(6) ##STR00012##

(7) All materials were commercially available from Sigma-Aldrich (Cas No.: 100080-82-8).

Preparation Example 3: Preparation of Precursor C

(8) ##STR00013##

(9) To a dried 250 mL schlenk flask was added 1.622 g (10 mmol) of fluorine, and 200 mL of THF was introduced thereto under argon. The THF solution was cooled down to 0 C., and then 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was slowly added dropwise. The reaction mixture was slowly warmed up to room temperature and stirred until the next day. To another 250 mL schlenk flask were added 1.2 mL (10 mmol, Fw 129.06, d 107 g/mL) of dichlorodimethylsilicone and 30 mL of hexane, the schlenk flask was cooled down to 78 C., and then lithiated solution was added dropwise thereto. After the addition was completed, the mixture was slowly warmed up to room temperature and stirred for one day. At the same time, 10 mmol of tetramethylcyclopentadiene was cooled down to 0 C. under THF dyddao, then 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was slowly added dropwise and subjected to lithiation reaction for one day. The next day, chloro(9H-fluoren-9-yl)dimethylsilane and lithiated 4-methylcyclopentadiene flask were combined with cannula at room temperature. At this time, the direction supplied to the cannula does not affect the experiment. After stirring for one day, 50 mL of water was added to the flask, quenched, the organic layer was separated and dried over MgSO.sub.4. Thereby, 3.53 g (10.25 mmol, 100%) of ligand of a yellow powder was obtained.

(10) NMR standard purity (wt %)=100%

(11) Mw=344.56

(12) .sup.1H NMR (500 MHz, CDCl3): 0.36 (6H, s), 1.80 (6H, s), 1.94 (6H, s), 3.20 (1H, s), 4.09 (1H, s), 7.28-7.33 (4H, m), 7.52 (2H, d), 7.83 (2H, d)

(13) The ligand synthesized above was added to a 250 mL schlenk flask dried in an oven and dissolved in diethylether. Then, 2.1 equivalents (21.5 mmol, 8.6 mL) of n-BuLi solution was added thereto, and subjected to lithiation until the next day. The next day, the solvent diethylether was all evaporated under vacuum, and then hexane slurry was filtered through a schlink filter to obtain ligands in the form of a Li salt (yellow solid). This filtered Li salt was added to a new 250 mL schlenk flask, and a suspension containing 50 mL of toluene was prepared. In addition, 1 equivalents of ZrCl.sub.4 (THF).sub.2 was taken in a glove box and added to a 250 mL schlenk flask, and a suspension containing toluene was prepared. The above two flasks were cooled down to 78 C., and then ligand anion was slowly added to the Zr suspension. After the addition was completed, the reaction mixture was slowly warmed up to room temperature. After stirring for one day, toluene in the mixture was immediately filtered through a schlink filter under argon to obtain 3.551 g (6.024 mmol, 61.35% Yield) of catalyst precursor in the form of a filter cake.

(14) NMR standard purity (wt %)=85.6% (residual LiCl)

(15) Mw=504.68

(16) .sup.1H NMR (500 MHz, CDCl3): 1.30 (6H, s), 1.86 (6H, s), 1.95 (6H, s), 7.21 (2H, m), 7.53 (2H, m), 7.65 (2H, m), 8.06 (2H, m)

Preparation Example 4: Preparation of Precursor D

(17) ##STR00014##

(18) 2.8 g (10 mmol) of ditertbutylfluorene was dissolved in 4.8 mL of MTBE and 90 mL of hexane, 6.4 mL of 2.5 M n-BuLi hexane solution was added dropwise in an ice bath and stirred at room temperature overnight. 2.7 g (10 mmol) of the Si bridge compound was dissolved in 50 mL of hexane, the Flu-Li slurry was transferred into a dried ice/acetone bath for 30 minutes and stirred at room temperature overnight. At the same time, 2.3 g (10 mmol) of indenoindole was also dissolved in 50 mL of THF, 8.0 mL (20 mmol) of 2.5 M n-BuLi hexane solution was added dropwise into a dried ice/acetone bath, and stirred at room temperature overnight. Si reaction solution was sampled and dried. Then, the completion of the reaction was confirmed by NMR sampling in a glove box, and the indenoindole-Li solution was transferred in a dried ice/acetone bath. And the mixture was stirred at room temperature overnight. After the reaction, the mixture was extracted with ether/water and the residual moisture of the organic layer was dried over MgSO.sub.4. The mixture obtained by filtering was evaporated under vacuum-reduced pressure to remove the solvent. Thereby, 7.3 g (10.3 mmol, 103%) of ligand was obtained.

(19) .sup.1H NMR (500 MHz, d-benzene): 0.03, 0.04 (3H, d). 0.46-0.90 (6H, m), 1.06 (2H, m), 1.13 (9H, s), 1.28-1.33 (18H, m), 1.62 (2H, m), 2.49 (3H, s), 3.22 (2H, m), 3.35, 3.54 (1H, d), 3.75 (1H, d), 4.15 (1H, d), 7.02 (1H, d), 7.10 (2H, m), 7.19-7.49 (8H, m), 7.71 (1H, m), 7.78-7.86 (2H, m)

(20) 4 equivalents of MTBE and 80 mL of toluene were used as the solvent for the metallization, and 2.4 g (28.0%) of purple solid was obtained from 7.3 g (10.3 mmol) of the ligand.

(21) NMR standard purity (wt %)=100%

(22) Mw=856.2

(23) .sup.1H NMR (500 MHz, CDCl3): 0.96 (9H, s), 1.17 (9H, s), 1.28-1.62 (4H, m), 1.66 (3H, s), 1.82 (2H, m), 2.08 (2H, m), 2.23 (2H, m), 2.49 (3H, s), 3.35 (2H, t), 3.88 (3H, s), 6.73 (1H, t), 7.12 (3H, s), 7.25 (1H, d), 7.46 (2H, m), 7.61-7.68 (3H, m), 7.74 (1H, s), 7.84 (2H, m)

Preparation Example 5: Preparation of Precursor E

(24) ##STR00015##

(25) To a dried 250 mL schlenk flask were added 10.78 g (48.5 mmol) of 2-(6-tert-butoxyhexyl)cyclopenta-1,3-diene and 7.1 mL (2+ equiv.) of acetone in methanol solvent under argon. The solution was cooled down to 0 C. and 5.17 g (1.5 equiv., 72.7 mmol) of pyrrolidine was added dropwise. The reaction mixture was slowly warmed up to room temperature and stirred until the next day. 50 mL of water and acetic acid were added to the flask, stirred for about 30 minutes, and then worked up with ether. The organic layer was separated and dried over MgSO.sub.4 to obtain 8.2 g (31.25 mmol) of 2-(6-tert-butoxyhexyl)-5-(propan-2-ylidene)cyclopenta-1,3-diene. This was confirmed by NMR to be pure (64.4% yield).

(26) Under argon, 3.866 g (10 mmol) of 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorine was prepared in another 250 mL schlenk flask and dissolved in 40 mL of THF. The solution was cooled down to 0 C. and 4.8 mL (12 mmol) of 2.5 M n-BuLi hexane solution was added dropwise. The reaction mixture was slowly warmed up to room temperature and stirred until the next day. An aliquot of 2.6243 g (10 mmol) of 2-(6-tert-butoxyhexyl)-5-(propan-2-ylidene)cyclopenta-1,3-diene previously synthesized was dissolved in THF and added dropwise to the lithiated mixture, and the solution was stirred overnight. 50 mL of water was added to the flask, quenched and worked up with ether and water. The organic layer was separated and then dried over MgSO.sub.4. Thereby, 6.51 g (10.03 mmol, 100.3%) of the ligand was obtained.

(27) NMR standard purity (wt %)=100%

(28) Mw=649.04

(29) The ligand synthesized above was added to a 250 mL schlenk flask dried in an oven and dissolved in ether, then 2.1 equivalents of n-BuLi solution was added thereto, and subjected to lithiation until the next day.

(30) 2.1 equivalents of ZrCl.sub.4(THF).sub.2 was taken in a glove box and added to a 250 mL schlenk flask, and a suspension containing ether was prepared. The above two flasks were cooled down to 78 C., and then ligand anion was slowly added to the Zr suspension. After the addition was completed, the reaction mixture was slowly warmed up to room temperature. The ether solution was then filtered under argon and the filtered solid filter cake LiCl was removed. Then, the ether remaining in the filtrate was removed through vacuum-reduced pressure and hexane of volume equivalent to the previous solvent was added and subjected to recrystallization, but the catalyst precursor was soluble due to its high solubility in hexane. The hexane solvent was completely evaporated under vacuum-reduced pressure and the catalyst synthesis was confirmed by NMR. The yield and purity were confirmed by weighing and sampling in the glove box. Thereby, 6.66 g (8.23 mmol, 82.3% Yield) of red catalyst precursor was obtained.

(31) NMR standard purity (wt %)=100%

(32) Mw=809.16

(33) .sup.1H NMR (500 MHz, CDCl3): 1.13 (4H, m), 1.18 (20H, m), 1.35 (9H, m), 1.38 (11H, m), 1.54 (3H, s), 1.65-1.83 (9H, m), 3.33 (2H, m), 3.45 (2H, q), 3.98 (1H, s), 5.67, 5.98, 6.54, 6.97 (total 3H, s), 7.10 (1H, s), 7.41 (1H, s), 7.53 (1H, s), 7.63 (1H, s)

Preparation of Hybrid Supported Catalyst

Example 1

(34) To a 300 mL glass reactor was added 50 mL of toluene solution, and then 10 g of silica (Grace Davison, SP2410) was added, and the mixture was stirred while raising the reactor temperature to 40 C. 60 mL of 10 wt % methylaluminoxane (MAO)/toluene solution (Albemarle) was added, warmed up to 60 C., and then stirred at 200 rpm for 12 hours. After the reactor temperature was lowered to room temperature, stirring was stopped, and the reaction solution was allowed to settle for 10 minutes and decanted.

(35) 50 mL of toluene was added to the reactor, 0.50 g of the catalyst precursor A and 10 mL of toluene solution were added to the reactor and stirred at 200 rpm for 60 minutes. 0.5 g of the catalyst precursor D and 10 mL of toluene solution were added to the reactor and stirred at 200 rpm for 12 hours. Stirring was stopped, and the reaction solution was allowed to settle for 30 minutes and decanted. To the reactor, 100 mL of hexane was added, hexane slurry was transferred to 250 mL schlink flask, and hexane solution was decanted. It was dried under reduced pressure at room temperature for 3 hours.

Example 2

(36) To a 300 mL glass reactor was added 50 mL of toluene solution, and then 10 g of silica (Grace Davison, SP2410), the mixture was stirred while raising the reactor temperature to 40 C. 60 mL of 10 wt % methylaluminoxane (MAO)/toluene solution (Albemarle) was added, warmed up to 60 C., and then stirred at 200 rpm for 12 hours. After the reactor temperature was lowered to room temperature, stirring was stopped, and the solution was allowed to settle for 10 minutes and the toluene solution was decanted.

(37) 100 mL of toluene was added, and the mixture was stirred for 10 minutes. Stirring was stopped, and then the reaction solution was allowed to settle for 10 minutes and toluene solution was decanted. 50 mL of toluene was added to the reactor, 0.50 g of the catalyst precursor A and 10 mL of toluene solution were added to the reactor and stirred at 200 rpm for 60 minutes. 0.5 g of the catalyst precursor B and 10 mL of toluene solution were added to the reactor and stirred at 200 rpm for 12 hours. 0.5 g of the catalyst precursor D and 10 mL of toluene solution were added to the reactor and stirred at 200 rpm for 12 hours. Stirring was stopped, and then the reaction solution was allowed to settle for 10 minutes and decanted. To the reactor, 100 mL of hexane was added, hexane slurry was transferred to 250 mL schlink flask, and hexane solution was decanted. It was dried under reduced pressure at room temperature for 3 hours.

Example 3

(38) A hybrid supported catalyst was prepared in the same manner as in Example 2, except that the catalyst precursor C was used instead of the catalyst precursor B in Example 2.

Example 4

(39) A hybrid supported catalyst was prepared in the same manner as in Example 2, except that the catalyst precursor E was used instead of the catalyst precursor B in Example 2.

Comparative Example 1

(40) Ziegler-Natta catalyst was prepared.

Comparative Example 2

(41) A hybrid supported catalyst was prepared in the same manner as in Example 2, except that the catalyst precursor E was used instead of the catalyst precursor D in Example 1.

Experimental Example

(42) Each of the catalysts prepared in Examples and Comparative Examples was weighed in a glove box, added to a 50 mL glass bottle. Then, the bottle was sealed with a rubber diaphragm and taken out of the glove box to prepare a catalyst to be added into the polymerization.

(43) Polymerization was carried out in a 600 mL temperature-controllable metal alloy reactor which was equipped with a mechanical stirrer and available at high pressure. To this reactor were added 400 mL of hexane containing 1.0 mmol triethylaluminum, the catalysts prepared above without contact with air and 1-hexene was added at 80 C. Polymerization was carried out for 1 hour, while continuously providing a gaseous ethylene monomer and hydrogen monomer (0.3% relative to ethylene) at a pressure of 9 Kgf/cm.sup.2. The termination of the polymerization was completed by first stopping the reaction and then removing the unreacted ethylene by evacuating. The obtained polymer product was filtered to remove the solvent and dried in a vacuum oven at 80 C. for 4 hours.

(44) The physical properties of the obtained polymer were measured by the following methods.

(45) 1) Catalyst activity: The catalyst activity was determined by dividing the weight (kg) of the obtained polymer by the weight (g) of silica used.

(46) 2) Density: ASTM 1505

(47) 3) MFR.sub.2.16: Measuring temperature 190 C., 2.16 kg load, ASTM 1238

(48) 4) MFRR(MFR.sub.21.6/MFR.sub.5): MFRR was determined by dividing MFR.sub.21.6 (measuring temperature 190 C., 21.6 kg load, ASTM 1238) by MFR.sub.5 (measuring temperature 190 C., 5 kg load, ASTM 1238).

(49) 5) Mn, Mw, MWD: The sample was dissolved in 1,2,4-trichlorobenzene containing 0.0125% of BHT at 160 C. for 10 hours using PL-SP260 and subjected to pretreatment, and the number average molecular weight, and weight average molecular weight were measured by PL-GPC220 at 160 C. as a measuring temperature. The molecular weight distribution was represented by the ratio of the weight average molecular weight to the number average molecular weight.

(50) 6) Spiral flow length: The measurement was carried out by using ENGEL 150 ton injection machine and setting the mold thickness to 1.5 mm, the injection temperature to 190 C., the mold temperature to 50 C., and the injection pressure to 90 bar.

(51) The results are shown in Table 1 below.

(52) TABLE-US-00001 TABLE 1 Catalytic Molecular Spiral activity Density MFR.sub.2.16 Molecular weight Flow Catalyst (kgPE/gSiO.sub.2) (g/cm.sup.3) (g/10 min) MFRR weight distribution (cm) Example 1 A/D 6.3 0.951 0.17 6.7 140K 10.6 15.2 Example 2 A/B/D 6.8 0.952 0.12 7.2 98K 10.8 16.5 Example 3 A/C/D 7.1 0.952 0.22 7.3 170K 10.7 16.9 Example 4 A/D/E 5.6 0.955 0.05 5.9 200K 10.5 13.8 Comparative Z/N 0.952 0.89 3.9 150K 10.2 12.5 Example 1 Comparative A/E 5.3 0.954 2.00 3.4 85K 9.8 10.0 Example 2