WO2022124694A1 - 올레핀계 중합체, 그로부터 제조된 필름 및 그 제조방법 - Google Patents
올레핀계 중합체, 그로부터 제조된 필름 및 그 제조방법 Download PDFInfo
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- WO2022124694A1 WO2022124694A1 PCT/KR2021/018076 KR2021018076W WO2022124694A1 WO 2022124694 A1 WO2022124694 A1 WO 2022124694A1 KR 2021018076 W KR2021018076 W KR 2021018076W WO 2022124694 A1 WO2022124694 A1 WO 2022124694A1
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- olefin
- olefinic
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- 229920000642 polymer Polymers 0.000 title claims abstract description 96
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 78
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 9
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 9
- 150000003623 transition metal compounds Chemical class 0.000 claims description 56
- 150000001875 compounds Chemical class 0.000 claims description 49
- 239000000155 melt Substances 0.000 claims description 40
- 238000001125 extrusion Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 24
- -1 cationic Lewis base Chemical class 0.000 claims description 24
- 239000000178 monomer Substances 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 229910052735 hafnium Inorganic materials 0.000 claims description 11
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
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- 238000004519 manufacturing process Methods 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
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- 239000010936 titanium Substances 0.000 claims description 6
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- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 238000012685 gas phase polymerization Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 229910052795 boron group element Inorganic materials 0.000 claims description 3
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- 125000004404 heteroalkyl group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
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- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
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- 239000000243 solution Substances 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
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- 239000004215 Carbon black (E152) Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
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- 229910052723 transition metal Inorganic materials 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
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- RSPAIISXQHXRKX-UHFFFAOYSA-L 5-butylcyclopenta-1,3-diene;zirconium(4+);dichloride Chemical compound Cl[Zr+2]Cl.CCCCC1=CC=C[CH-]1.CCCCC1=CC=C[CH-]1 RSPAIISXQHXRKX-UHFFFAOYSA-L 0.000 description 1
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- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
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- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
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- C08F2500/18—Bulk density
Definitions
- the present invention relates to an olefin-based polymer, a film prepared therefrom, and a method for preparing the same. Specifically, the present invention relates to an olefin-based polymer having excellent processability, an olefin-based polymer film prepared therefrom and having excellent mechanical strength, particularly, drop impact strength, and a method for manufacturing the same.
- a metallocene catalyst which is one of the catalysts used to polymerize olefins, is coordinated with a transition metal or a transition metal halogen compound with ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl. As a bound compound, it has a sandwich structure in its basic form.
- the active site metal component is dispersed on an inactive solid surface and thus the properties of the active site are not uniform, the metallocene catalyst has a uniform structure. Since it is a compound with The polymer polymerized with such a metallocene catalyst has a narrow molecular weight distribution, a uniform distribution of comonomers, and higher copolymerization activity than the Ziegler-Natta catalyst.
- linear low-density polyethylene is prepared by copolymerizing ethylene and alpha-olefin at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution and short chain branch (SCB) of a constant length. and generally do not have a long chain branch (LCB).
- SCB short chain branch
- Films made of linear low-density polyethylene have the characteristics of general polyethylene, high breaking strength and elongation, and excellent tear strength and impact strength. It is widely used in stretch films and overlap films, which are difficult to apply.
- linear low-density polyethylene prepared by a metallocene catalyst tends to have poor processability due to a narrow molecular weight distribution.
- Another object of the present invention is to provide an olefin-based polymer film prepared from the above olefin-based polymer and having excellent mechanical strength, particularly, drop impact strength.
- Another object of the present invention is to provide a method for preparing the olefin-based polymer and the olefin-based polymer film.
- the density is 0.9 ⁇ 0.95 g / cm3;
- Melt index (I 2.16 ) measured at 190°C under a load of 2.16 kg is 0.1 to 5.0 g/10 min;
- a shear thinning index defined by Equation 1 below is 8 to 15;
- an olefin-based polymer having an extrusion torque of 270 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom is 700 g or more, preferably 700 to 2,000 g based on a thickness of 50 ⁇ m.
- An olefinic polymer having an impact strength (Type B) is provided.
- ⁇ 0 and ⁇ 500 are complex viscosities at frequencies of 0.1 rad/s and 500 rad/s, respectively.
- the olefin-based polymer has (1) a density of 0.915 to 0.945 g/cm 3 ; (2) Melt index (I 2.16 ) measured at 190°C under a load of 2.16 kg is 0.1 to 5.0 g/10 min; (3) a melt flow ratio (MFR) of 20 or more at 190°C with a melt flow rate (I 21.6 ) measured under a load of 21.6 kg and a melt index (I 2.16 ) measured under a load of 2.16 kg; (4) a shear thinning index defined by Equation 1 is 9 to 15; (5) An olefin-based polymer having an extrusion torque of 260 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom may have a drop impact strength (type B) of 700 g or more based on a thickness of 50 ⁇ m have.
- type B drop impact strength
- the olefin-based polymer comprises (1) a density of the olefin-based polymer of 0.915 to 0.942 g/cm 3 ; (2) a melt index of 0.5 to 3.5 g/10 min, measured at 190°C with a load of 2.16 kg; (3) an MFR of 20 to 50; (4) the shear thinning index defined by Equation 1 is 9 to 12; (5)
- the extrusion load may be 200 to 255 Nm at an extrusion amount of 5.8 to 5.9 kg/hr.
- the olefin-based polymer may include at least one first transition metal compound represented by Formula 1 below; And it can be prepared by polymerizing the olefinic monomer in the presence of a hybrid catalyst comprising at least one second transition metal compound selected from the compound represented by the formula (2) and the compound represented by the following formula (3).
- M 1 and M 2 are different and each independently titanium (Ti), zirconium (Zr) or hafnium (Hf),
- each X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl or C 1-20 alkylamido;
- R 1 to R 10 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1 -20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl , R 1 to R 10 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring.
- M 1 and M 2 are different from each other and each is zirconium or hafnium
- X is each halogen or C 1-20 alkyl
- R 1 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
- M 1 may be hafnium
- M 2 may be zirconium
- X may be chlorine or methyl
- the first transition metal compound is at least one of the transition metal compounds represented by Formulas 1-1 and 1-2 below
- the second transition metal compound is represented by Formulas 2-1, 2-2 and It may be at least one of the transition metal compounds represented by 3-1.
- Me is a methyl group.
- the molar ratio of the first transition metal compound to the second transition metal compound ranges from 100:1 to 1:100.
- the above catalyst may include at least one cocatalyst selected from the group consisting of a compound represented by Formula 4, a compound represented by Formula 5, and a compound represented by Formula 6 below.
- n is an integer of 2 or more
- R a is a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen
- D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen. Or a C 1-20 alkoxy group,
- L is a neutral or cationic Lewis base
- [LH] + and [L] + are a Bronsted acid
- Z is a group 13 element
- A is each independently substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group.
- the above catalyst may further include a carrier supporting a transition metal compound, a cocatalyst compound, or both.
- the gastric carrier may include at least one selected from the group consisting of silica, alumina and magnesia.
- the total amount of the hybrid transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the total amount of the cocatalyst compound supported on the carrier is 2 to 15 mmole based on 1 g of the carrier.
- the olefinic polymer is a copolymer of an olefinic monomer and an olefinic comonomer.
- the olefinic monomer is ethylene
- the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 - It may be at least one selected from the group consisting of undecene, 1-dodecene, 1-tetradecene and 1-hexadecene.
- the olefinic polymer is a linear low density polyethylene wherein the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene.
- a hybrid catalyst comprising at least one second transition metal compound selected from the compound represented by Formula 2 and the compound represented by Formula 3 to obtain an olefinic polymer
- the density of the olefin-based polymer is 0.9 to 0.95 g/cm 3 , preferably 0.91 to 0.945 g/cm 3 ;
- melt flow ratio (MFR) of the melt index (I 21.6 ) measured at 190°C under a load of 21.6 kg and the melt index (I 2.16 ) measured at a load of 2.16 kg is 20 or more, preferably 22 or more ;
- a shear thinning index defined by Equation 1 below is 8 to 15, preferably 9 to 15;
- an olefin-based polymer having an extrusion torque of 270 Nm or less, preferably 260 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom is 700 g or more based on a thickness of 50 ⁇ m, preferably has a drop impact strength (type B) of 700 to 2,000 g, is provided a method for producing an olefin-based polymer.
- the polymerization of the olefinic monomer may be carried out by gas phase polymerization, and specifically, the polymerization of the olefinic monomer may be carried out in a gas phase fluidized bed reactor.
- the olefin-based polymer according to an embodiment of the present invention has excellent processability, and a film prepared therefrom, particularly a linear low-density polyethylene film, has excellent mechanical strength, particularly, drop impact strength.
- FIG. 1 is a graph showing the complex viscosity according to the frequency of the olefinic polymers of Examples 1 and 2 and Comparative Example 1.
- FIG. 1 is a graph showing the complex viscosity according to the frequency of the olefinic polymers of Examples 1 and 2 and Comparative Example 1.
- Figure 2 is a graph showing the extrusion load (torque) according to the extrusion amount of the olefin-based polymer of Examples 1 and 2 and Comparative Example 1.
- the density is 0.9 ⁇ 0.95 g / cm3;
- Melt index (I 2.16 ) measured at 190°C under a load of 2.16 kg is 0.1 to 5.0 g/10 min;
- a shear thinning index defined by Equation 1 below is 8 to 15;
- an olefin-based polymer having an extrusion torque of 270 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom is 700 g or more, preferably 700 to 2,000 g based on a thickness of 50 ⁇ m.
- An olefinic polymer having an impact strength (type B) is provided.
- the olefin-based polymer has (1) a density of 0.915 to 0.945 g/cm 3 ; (2) Melt index (I 2.16 ) measured at 190°C under a load of 2.16 kg is 0.1 to 5.0 g/10 min; (3) a melt flow ratio (MFR) of 20 or more at 190°C with a melt flow rate (I 21.6 ) measured under a load of 21.6 kg and a melt index (I 2.16 ) measured under a load of 2.16 kg; (4) a shear thinning index defined by Equation 1 is 9 to 15; (5) An olefin-based polymer having an extrusion torque of 260 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom may have a drop impact strength (type B) of 700 g or more based on a thickness of 50 ⁇ m have.
- type B drop impact strength
- the olefin-based polymer comprises (1) a density of the olefin-based polymer of 0.915 to 0.942 g/cm 3 ; (2) a melt index of 0.5 to 3.5 g/10 min, measured at 190°C with a load of 2.16 kg; (3) an MFR of 20 to 50; (4) the shear thinning index defined by Equation 1 is 9 to 12; (5)
- the extrusion load may be 200 to 255 Nm at an extrusion amount of 5.8 to 5.9 kg/hr.
- the olefinic polymer has a density of 0.9-0.95 g/cm 3 .
- the density of the olefin-based polymer may be 0.91 to 0.945 g/cm 3 , 0.915 to 0.945 g/cm 3 , 0.91 to 0.93 g/cm 3 , 0.915 to 0.942 g/cm 3 or 0.915 to 0.925 g/cm 3 .
- the olefin-based polymer has a melt index (I 2.16 ) of 0.1 to 5.0 g/10 min, measured at 190° C. under a load of 2.16 kg.
- the melt index of the olefin-based polymer measured at 190° C. under a load of 2.16 kg may be 0.3 to 4.0 g/10 min, 0.5 to 3.5 g/10 min, or 0.5 to 3.0 g/10 min.
- the olefin-based polymer has a melt flow ratio (MFR) of a melt index (I 21.6 ) measured at 190° C. under a load of 21.6 kg and a melt index (I 2.16 ) measured at a load of 2.16 kg more than 20
- MFR melt flow ratio
- I 21.6 melt index measured at 190° C. under a load of 21.6 kg
- I 2.16 melt index measured at a load of 2.16 kg more than 20
- the MFR of the olefin-based polymer may be 22 or more or 20-50.
- the olefin-based polymer has a shear thinning index defined by Equation 1 below from 8 to 15.
- the shear thinning index of the olefinic polymer may be 9 to 15 or 9 to 12.
- ⁇ 0 and ⁇ 500 are complex viscosities at frequencies of 0.1 rad/s and 500 rad/s, respectively.
- Polymers have properties that are intermediate between that of a perfectly elastic material and a viscous liquid in a molten state, which is called viscoelasticity. That is, when a polymer receives a shear stress in a molten state, the deformation is not proportional to the shear stress, and also has a characteristic that the viscosity changes according to the shear stress. It is understood that these properties are due to the large molecular size and complex intermolecular structure of polymers.
- the shear thinning phenomenon refers to a phenomenon in which the viscosity of a polymer decreases as the shear rate increases.
- the polymer may have excellent physical properties and processability.
- the olefin-based polymer has an extrusion torque of 270 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr.
- the extrusion torque of the olefinic polymer is 260 Nm or less or 200 to 255 Nm at an extrusion amount of 5.8 to 5.9 kg/hr.
- the film prepared from the olefin-based polymer has a drop impact strength of 700 g or more based on a thickness of 50 ⁇ m.
- the film prepared from the olefin-based polymer may have a drop impact strength of 700 to 2,000 g based on a thickness of 50 ⁇ m.
- the olefin-based polymer according to the embodiment of the present invention has a relatively wide molecular weight distribution, and since there are relatively many short-chain branches in the high molecular weight component, the mechanical strength of the olefin-based polymer film prepared therefrom, especially the drop impact strength, is excellent. it is understood that
- the olefin-based polymer film can be effectively used as a stretch film, an overlap film, a ramie, a silage wrap, an agricultural film, and the like.
- a method for forming a film from an olefin-based polymer according to an embodiment of the present invention is not particularly limited, and a forming method known in the art to which the present invention pertains may be used.
- the above-described olefin-based polymer may be processed by a conventional method such as blown film molding, extrusion molding, and casting molding to prepare an olefin-based polymer film. Among them, blown film molding is most preferable.
- the olefin-based polymer may include at least one first transition metal compound represented by Formula 1 below; And it can be prepared by polymerizing the olefinic monomer in the presence of a hybrid catalyst comprising at least one second transition metal compound selected from the compound represented by the formula (2) and the compound represented by the following formula (3).
- M 1 and M 2 are different from each other and each independently represent titanium (Ti), zirconium (Zr), or hafnium (Hf).
- M 1 and M 2 may be different from each other and may be zirconium or hafnium, respectively.
- M 1 may be hafnium and M 2 may be zirconium.
- each X is independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido or C 6-20 arylamido.
- each X may be halogen or C 1-20 alkyl.
- X may be chlorine or methyl.
- R 1 to R 10 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1 -20 alkyl C 6-20 aryl, substituted or unsubstituted C 6-20 aryl C 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl , where R 1 to R 10 may be each independently connected to adjacent groups to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring. Specifically, R 1 to R
- M 1 and M 2 are different from each other and each is zirconium or hafnium
- X is each halogen or C 1-20 alkyl
- R 1 to R 10 may each be hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 1-20 alkenyl, or substituted or unsubstituted C 6-20 aryl.
- M 1 may be hafnium
- M 2 may be zirconium
- X may be chlorine or methyl
- the first transition metal compound is at least one of the transition metal compounds represented by Formulas 1-1 and 1-2 below
- the second transition metal compound is represented by Formulas 2-1, 2-2 and It may be at least one of the transition metal compounds represented by 3-1.
- Me is a methyl group.
- the molar ratio of the first transition metal compound to the second transition metal compound ranges from 100:1 to 1:100.
- the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 50:1 to 1:50.
- the molar ratio of the first transition metal compound to the second transition metal compound is in the range of 10:1 to 1:10.
- the above catalyst may include at least one cocatalyst compound selected from the group consisting of a compound represented by Formula 4 below, a compound represented by Formula 5, and a compound represented by Formula 6 below. .
- n is an integer of 2 or more
- R a may be a halogen atom, a C 1-20 hydrocarbon, or a halogen-substituted C 1-20 hydrocarbon.
- R a may be methyl, ethyl, n -butyl or isobutyl.
- D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, a C 1-20 hydrocarbon group, or a C 1-20 hydrocarbon group substituted with a halogen. or a C 1-20 alkoxy group.
- R b , R c and R d may each independently be methyl or isobutyl
- D is boron (B)
- R b , R c and R d are each may be pentafluorophenyl.
- L is a neutral or cationic Lewis base
- [LH] + and [L] + are a Bronsted acid
- Z is a group 13 element
- A is each independently substituted or unsubstituted C 6 It is a -20 aryl group or a substituted or unsubstituted C 1-20 alkyl group.
- [LH] + may be a dimethylanilinium cation
- [Z(A) 4 ] - may be [B(C 6 F 5 ) 4 ] -
- [L] + may be [(C 6 H) 5 ) 3 C] + .
- examples of the compound represented by the above formula (4) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferred, but is not limited thereto.
- Examples of the compound represented by the above formula (5) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri- s -butylaluminum, tricyclopentylaluminum , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like, and trimethylaluminum, triethylaluminum and triisobutylaluminum are preferred, but are not limited there
- Examples of the compound represented by the above formula (6) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra( p -tolyl) Boron, trimethylammonium tetra( o , p -dimethylphenyl)boron, tributylammonium tetra( p -trifluoromethylphenyl)boron, trimethylammonium tetra( p -trifluoromethylphenyl)boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron
- the above catalyst may further include a carrier supporting a transition metal compound, a cocatalyst compound, or both.
- the carrier may support both the transition metal compound and the promoter compound.
- the carrier may include a material containing a hydroxyl group on the surface, preferably dried to remove moisture from the surface, a material having a high reactivity hydroxyl group and siloxane group may be used.
- the carrier may include at least one selected from the group consisting of silica, alumina and magnesia. Specifically, silica dried at high temperature, silica-alumina, silica-magnesia, and the like may be used as the carrier, and these are typically oxides such as Na 2 O, K 2 CO 3 , BaSO 4 , and Mg(NO 3 ) 2 . , carbonate, sulfate, and nitrate components. They may also contain carbon, zeolites, magnesium chloride, and the like.
- the carrier is not limited thereto, and is not particularly limited as long as it can support the transition metal compound and the promoter compound.
- the carrier may have an average particle size of 10-250 ⁇ m, preferably an average particle size of 10-150 ⁇ m, and more preferably 20-100 ⁇ m.
- the micropore volume of the carrier may be 0.1-10 cc/g, preferably 0.5-5 cc/g, and more preferably 1.0-3.0 cc/g.
- the specific surface area of the carrier may be 1 to 1,000 m2/g, preferably 100 to 800 m2/g, and more preferably 200 to 600 m2/g.
- the carrier may be silica.
- the silica may have a drying temperature of 200 to 900°C.
- the drying temperature may be preferably 300 to 800°C, more preferably 400 to 700°C. If the drying temperature is less than 200 °C, there is too much moisture, the surface moisture and the cocatalyst compound react, and if it exceeds 900 °C, the structure of the carrier may be collapsed.
- the concentration of hydroxyl groups in the dried silica may be 0.1-5 mmole/g, preferably 0.7-4 mmole/g, and more preferably 1.0-2 mmole/g.
- the hydroxyl group concentration is less than 0.1 mmole/g, the supported amount of the first cocatalyst compound is lowered, and when it exceeds 5 mmole/g, a problem in that the catalyst component is deactivated may occur.
- the total amount of the transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier.
- the total amount of the promoter compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier.
- One type or two or more types of carriers may be used.
- both the transition metal compound and the promoter compound may be supported on one type of support, or the transition metal compound and the promoter compound may be supported on two or more types of support, respectively.
- only one of the transition metal compound and the promoter compound may be supported on the carrier.
- a physical adsorption method or a chemical adsorption method may be used as a method of supporting a transition metal compound and/or a cocatalyst compound that can be used in a catalyst for olefin polymerization.
- the physical adsorption method is a method of drying a solution in which a transition metal compound is dissolved in contact with a carrier, a method in which a solution in which a transition metal compound and a cocatalyst compound are dissolved, is contacted with a carrier and then drying, or a transition metal compound
- the dissolved solution was brought into contact with the carrier and dried to prepare a carrier on which the transition metal compound was supported.
- the solution in which the cocatalyst compound was dissolved was contacted with the carrier and dried to prepare a carrier on which the cocatalyst compound was supported. After that, it may be a method of mixing them, or the like.
- the chemical adsorption method is a method in which a promoter compound is first supported on the surface of a carrier, and then a transition metal compound is supported on the promoter compound, or a functional group on the surface of the support (for example, in the case of silica, a hydroxyl group on the silica surface (-OH) )) and a method of covalently bonding the catalyst compound and the like.
- the olefin-based polymer may be a homopolymer of an olefin-based monomer or a copolymer of an olefin-based monomer and a comonomer.
- the olefinic polymer is a copolymer of an olefinic monomer and an olefinic comonomer.
- the olefinic monomer is C 2-20 alpha-olefin ( ⁇ -olefin), C 1-20 diolefin (diolefin), C 3-20 cycloolefin and C 3-20 cyclodiolefin. At least one selected from the group consisting of.
- the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 - may be dodecene, 1-tetradecene, 1-hexadecene, etc.
- the olefinic polymer may be a homopolymer including only one type of the olefinic monomer exemplified above, or a copolymer including two or more types.
- the olefin-based polymer may be a copolymer in which ethylene and C 3-20 alpha-olefin are copolymerized.
- the olefinic polymer may be a linear low density polyethylene wherein the olefinic monomer is ethylene and the olefinic comonomer is 1-hexene.
- the content of ethylene is 55 to 99.9 weight%, and it is more preferable that it is 90 to 99.9 weight%.
- the content of the alpha-olefin-based comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.
- At least one first transition metal compound represented by the following formula (1) And obtaining an olefinic polymer by polymerizing an olefinic monomer in the presence of a hybrid catalyst comprising at least one second transition metal compound selected from the compound represented by Formula 2 below and the compound represented by Formula 3 below
- a method for producing an olefin-based polymer is provided.
- M 1 , M 2 , X and R 1 to R 10 are the same as described in the above olefin-based polymer.
- the olefin-based polymer prepared by the manufacturing method according to an embodiment of the present invention has (1) a density of 0.9 to 0.95 g/cm 3 ; (2) Melt index (I 2.16 ) measured at 190°C under a load of 2.16 kg is 0.1 to 5.0 g/10 min; (3) a melt flow ratio (MFR) of 20 or more at 190°C with a melt flow rate (I 21.6 ) measured under a load of 21.6 kg and a melt index (I 2.16 ) measured under a load of 2.16 kg; (4) a shear thinning index defined by Equation 1 below is 8 to 15; (5) An olefin-based polymer having an extrusion torque of 270 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom has a drop impact strength (type B) of 700 g or more based on a thickness of 50 ⁇ m.
- type B drop impact strength
- ⁇ 0 and ⁇ 500 are complex viscosities at frequencies of 0.1 rad/s and 500 rad/s, respectively.
- the olefin-based polymer has (1) a density of 0.915 to 0.945 g/cm 3 ; (2) Melt index (I 2.16 ) measured at 190°C under a load of 2.16 kg is 0.1 to 5.0 g/10 min; (3) a melt flow ratio (MFR) of 20 or more at 190°C with a melt flow rate (I 21.6 ) measured under a load of 21.6 kg and a melt flow rate (I 2.16 ) measured under a load of 2.16 kg; (4) a shear thinning index defined by Equation 1 is 9 to 15; (5) An olefin-based polymer having an extrusion torque of 260 Nm or less at an extrusion amount of 5.8 to 5.9 kg/hr, and a film prepared therefrom can have a drop impact strength (type B) of 700 g or more based on a thickness of 50 ⁇ m have.
- type B drop impact strength
- the olefin-based polymer comprises (1) a density of the olefin-based polymer of 0.915 to 0.942 g/cm 3 ; (2) a melt index of 0.5 to 3.5 g/10 min, measured at 190°C with a load of 2.16 kg; (3) an MFR of 20 to 50; (4) the shear thinning index defined by Equation 1 is 9 to 12; (5)
- the extrusion load may be 200 to 255 Nm at an extrusion amount of 5.8 to 5.9 kg/hr.
- the olefin-based polymer may be polymerized by, for example, a polymerization reaction such as free radical, cationic, coordination, condensation, and addition. However, it is not limited thereto.
- the olefin-based polymer may be prepared by a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method.
- the polymerization of the olefinic monomer may be carried out by gas phase polymerization, and specifically, the polymerization of the olefinic monomer may be carried out in a gas phase fluidized bed reactor.
- the solvent that can be used include a C 5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof; aromatic hydrocarbon solvents such as toluene and benzene; hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; and mixtures thereof, but is not limited thereto.
- a C 5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof
- aromatic hydrocarbon solvents such as toluene and benzene
- hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene
- mixtures thereof but is not limited thereto.
- transition metal compound of Formula 1-1 bis(n-propylcyclopentadienyl) hafnium dichloride
- transition metal compound of Formula 2-1 bis(n-butylcyclopentadienyl) zirconium dichloride
- An ethylene/1-hexene copolymer was prepared in the presence of the supported catalyst obtained in Preparation Example 1 using a gas phase fluidized bed reactor.
- the partial pressure of ethylene in the reactor was maintained at about 15 kg/cm 2 , and the polymerization temperature was maintained at 70-90°C.
- Example 1 Example 2 Polymerization temperature (°C) 75.4 80.9 Catalyst injection amount (g/h) 2.0 1.4 Hydrogen injection amount (g/h) 2.22 2.34 1-Hexene injection (kg/h) 1.60 1.63 Hydrogen/Ethylene Concentration (%) Ratio 0.047 0.048 1-Hexene/Ethylene Concentration (%) Ratio 2.096 1.993
- the melt index was measured at 190°C under a load of 21.6 kg and a load of 2.16 kg, and the ratio (MI 21.6 /MI 2.16 ) was obtained.
- the frequency-dependent complex viscosity was measured using Anton Parr's MCR702 at 190°C in a frequency range of 0.1 to 500 rad/s and a strain of 5%.
- the extrusion load according to the extrusion amount was measured using Collin's Gottfert under the conditions of screw rpm of 20-80 and extrusion amount of 1.4-5.8 kg/hr at 190°C.
- each resin of Examples and Comparative Examples was prepared into a film having a thickness of 50 ⁇ m through a 40 mm blown film extruder (40 mm ⁇ screw, 75 mm ⁇ die, 2 mm die gap).
- BUR blow-up ratio
- a 50 ⁇ m thick film was measured according to ASTM D1709 B type.
- Example 1 Comparative Example 1 density g/cm3 0.9180 0.9205 0.9198 MI (I 2.16 ) g/10 min 0.98 1.06 1.01 MFI (I 21.6 ) g/10 min 26.0 24.9 16.6 MFR - 26.5 23.5 16.4 Shear Thinning Index - 10.5 9.1 7.3 extrusion load (Nm, 5.8 ⁇ 5.9 kg/hr) - 232.4 254.9 278.3 drop impact strength g 1,560 770 670
- the olefin-based polymer according to an embodiment of the present invention has excellent processability, and the olefin-based polymer film prepared therefrom, specifically, a linear low-density polyethylene film, has excellent mechanical strength, particularly, drop impact strength.
- the present invention can provide an olefin-based polymer having excellent processability and a film prepared therefrom and having excellent mechanical strength, particularly, drop impact strength.
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Abstract
Description
실시예 1 | 실시예 2 | |
중합온도(℃) | 75.4 | 80.9 |
촉매 주입량(g/h) | 2.0 | 1.4 |
수소 주입량(g/h) | 2.22 | 2.34 |
1-헥센 주입량(kg/h) | 1.60 | 1.63 |
수소/에틸렌 농도(%) 비 | 0.047 | 0.048 |
1-헥센/에틸렌 농도(%) 비 | 2.096 | 1.993 |
단위 | 실시예 1 | 실시예 2 | 비교예 1 | |
밀도 | g/㎤ | 0.9180 | 0.9205 | 0.9198 |
MI (I2.16) | g/10분 | 0.98 | 1.06 | 1.01 |
MFI (I21.6) | g/10분 | 26.0 | 24.9 | 16.6 |
MFR | - | 26.5 | 23.5 | 16.4 |
전단 담화 지수 | - | 10.5 | 9.1 | 7.3 |
압출부하 (Nm, 5.8~5.9 kg/hr) |
- | 232.4 | 254.9 | 278.3 |
낙하 충격 강도 | g | 1,560 | 770 | 670 |
Claims (16)
- (1) 밀도가 0.9~0.95 g/㎤; (2) 190℃에서 2.16 kg 하중으로 측정되는 용융지수(I2.16)가 0.1~5.0 g/10분; (3) 190℃에서 21.6 kg의 하중으로 측정되는 용융지수(I21.6)와 2.16 kg 하중으로 측정되는 용융지수(I2.16)의 비(melt flow ratio; MFR)가 20 이상; (4) 아래 수학식 1로 정의되는 전단 담화 지수(shear thinning index)가 8~15; (5) 압출량 5.8~5.9 kg/hr에서 압출 부하(torque)가 270 Nm 이하인 올레핀계 중합체로서, 이로부터 제조되는 필름이 두께 50 ㎛ 기준으로 700 g 이상의 낙하충격 강도(B 타입)를 갖는, 올레핀계 중합체:[수학식 1]전단 담화 지수 = η0/η500여기서, η0과 η500은 각각 주파수 0.1 rad/s와 500 rad/s에서의 복소 점도이다.
- 제1항에 있어서, (1) 밀도가 0.915~0.945 g/㎤; (2) 190℃에서 2.16 kg 하중으로 측정되는 용융지수(I2.16)가 0.1~5.0 g/10분; (3) 190℃에서 21.6 kg의 하중으로 측정되는 용융지수(I21.6)와 2.16 kg 하중으로 측정되는 용융지수(I2.16)의 비(melt flow ratio; MFR)가 20 이상; (4) 수학식 1로 정의되는 전단 담화 지수(shear thinning index)가 9~15; (5) 압출량 5.8~5.9 kg/hr에서 압출 부하(torque)가 260 Nm 이하인 올레핀계 중합체.
- 제1항에 있어서, 아래 화학식 1로 표시되는 적어도 1종의 제1 전이금속 화합물; 및 아래 화학식 2로 표시되는 화합물과 아래 화학식 3으로 표시되는 화합물 중에서 선택되는 적어도 1종의 제2 전이금속 화합물을 포함하는 혼성 촉매의 존재하에 올레핀계 단량체를 중합하여 제조되는 올레핀계 중합체:[화학식 1][화학식 2][화학식 3]위 화학식 1 내지 화학식 3에서, M1과 M2는 서로 다르면서 각각 독립적으로 티타늄(Ti), 지르코늄(Zr) 또는 하프늄(Hf)이고,X는 각각 독립적으로 할로겐, C1-20 알킬, C2-20 알케닐, C2-20 알키닐, C6-20 아릴, C1-20 알킬 C6-20 아릴, C6-20 아릴 C1-20 알킬, C1-20 알킬아미도 또는 C6-20 아릴아미도이고,R1 내지 R10은 각각 독립적으로 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C2-20 알케닐, 치환 또는 비치환된 C6-20 아릴, 치환 또는 비치환된 C1-20 알킬 C6-20 아릴, 치환 또는 비치환된 C6-20 아릴 C1-20 알킬, 치환 또는 비치환된 C1-20 헤테로알킬, 치환 또는 비치환된 C3-20 헤테로아릴, 치환 또는 비치환된 C1-20 알킬아미도, 치환 또는 비치환된 C6-20 아릴아미도, 치환 또는 비치환된 C1-20 알킬리덴, 또는 치환 또는 비치환된 C1-20 실릴이되, R1 내지 R10은 각각 독립적으로 인접한 기가 연결되어 치환 또는 비치환된 포화 또는 불포화 C4-20 고리를 형성할 수 있다.
- 제3항에 있어서, M1과 M2가 서로 다르면서 각각 지르코늄 또는 하프늄이고, X가 각각 할로겐 또는 C1-20 알킬이고, R1 내지 R10이 각각 수소, 치환 또는 비치환된 C1-20 알킬, 치환 또는 비치환된 C1-20 알케닐, 또는 치환 또는 비치환된 C6-20 아릴인, 올레핀계 중합체.
- 제4항에 있어서, M1이 하프늄이고, M2가 지르코늄이고, X가 염소 또는 메틸인, 올레핀계 중합체.
- 제3항에 있어서, 제1 전이금속 화합물 대 제2 전이금속 화합물의 몰 비가 100:1~1:100의 범위인, 올레핀계 중합체.
- 제3항에 있어서, 촉매가 아래 화학식 4로 표현되는 화합물, 화학식 5로 표현되는 화합물 및 화학식 6으로 표현되는 화합물로 구성되는 군으로부터 선택되는 적어도 1종의 조촉매 화합물을 포함하는, 올레핀계 중합체.[화학식 4][화학식 5][화학식 6][L-H]+[Z(A)4]- 또는 [L]+[Z(A)4]-위 화학식 4에서, n은 2 이상의 정수이고, Ra는 할로겐 원자, C1-20 탄화수소기 또는 할로겐으로 치환된 C1-20 탄화수소기이고,위 화학식 5에서, D는 알루미늄(Al) 또는 보론(B)이고, Rb, Rc 및 Rd는 각각 독립적으로 할로겐 원자, C1-20 탄화수소기, 할로겐으로 치환된 C1-20 탄화수소기 또는 C1-20 알콕시기이며,위 화학식 6에서, L은 중성 또는 양이온성 루이스 염기이고, [L-H]+ 및 [L]+는 브뢴스테드 산이며, Z는 13족 원소이고, A는 각각 독립적으로 치환 또는 비치환된 C6-20 아릴기이거나 치환 또는 비치환된 C1-20 알킬기이다.
- 제8항에 있어서, 촉매가 전이금속 화합물, 조촉매 화합물 또는 둘 다를 담지하는 담체를 더 포함하는, 올레핀계 중합체.
- 제9항에 있어서, 담체가 실리카, 알루미나 및 마그네시아로 구성되는 군으로부터 선택되는 적어도 하나를 포함하는, 올레핀계 중합체.
- 제9항에 있어서, 담체에 담지되는 혼성 전이금속 화합물의 총량이 담체 1 g을 기준으로 0.001~1 mmole이고, 담체에 담지되는 조촉매 화합물의 총량이 담체 1 g을 기준으로 2~15 mmole인, 올레핀계 중합체.
- 제1항에 있어서, 올레핀계 중합체가 올레핀계 단량체와 올레핀계 공단량체의 공중합체인 올레핀계 중합체.
- 제12항에 있어서, 올레핀계 단량체가 에틸렌이고, 올레핀계 공단량체가 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센 및 1-헥사데센으로 구성되는 군으로부터 선택되는 하나 이상인 올레핀계 중합체.
- 제13항에 있어서, 올레핀계 중합체가 올레핀계 단량체가 에틸렌이고 올레핀계 공단량체가 1-헥센인 선형 저밀도 폴리에틸렌인 올레핀계 중합체.
- 아래 화학식 1로 표시되는 적어도 1종의 제1 전이금속 화합물; 및 아래 화학식 2로 표시되는 화합물과 아래 화학식 3으로 표시되는 화합물 중에서 선택되는 적어도 1종의 제2 전이금속 화합물을 포함하는 혼성 촉매의 존재하에 올레핀계 단량체를 중합하여 올레핀계 중합체를 얻는 단계를 포함하되, 올레핀계 중합체의 올레핀계 중합체의 (1) 밀도가 0.9~0.95 g/㎤; (2) 190℃에서 2.16 kg 하중으로 측정되는 용융지수(I2.16)가 0.1~5.0 g/10분; (3) 190℃에서 21.6 kg의 하중으로 측정되는 용융지수(I21.6)와 2.16 kg 하중으로 측정되는 용융지수(I2.16)의 비(melt flow ratio; MFR)가 20 이상; (4) 아래 수학식 1로 정의되는 전단 담화 지수(shear thinning index)가 8~15; (5) 압출량 5.8~5.9 kg/hr에서 압출 부하(torque)가 270 Nm 이하이며, 이로부터 제조되는 필름이 두께 50 ㎛ 기준으로 700 g 이상의 낙하충격 강도(B 타입)를 갖는, 올레핀계 중합체의 제조방법:[화학식 1][화학식 2][화학식 3][수학식 1]전단 담화 지수 = η0/η500위 수학식에서 η0과 η500은 각각 주파수 0.1 rad/s와 500 rad/s에서의 복소 점도이고, 위 화학식에서 M1, M2, X 및 R1 내지 R10은 제3항에서 정의한 바와 같다.
- 제15항에 있어서, 올레핀계 단량체의 중합이 기상 중합으로 수행되는, 올레핀계 중합체의 제조방법.
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US20050159300A1 (en) * | 2004-01-21 | 2005-07-21 | Jensen Michael D. | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
JP2015113282A (ja) * | 2013-12-09 | 2015-06-22 | 広栄化学工業株式会社 | ハフニウム化合物とジルコニウム化合物の混合組成物およびその製造方法 |
US20160362510A1 (en) * | 2014-02-11 | 2016-12-15 | Univation Technologies, Llc | Method to prepare ethylene copolymers |
WO2019027585A1 (en) * | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | MIXED CATALYSTS COMPRISING UNDRAWNED HAFNOCENES WITH -CH2-SIME3 FRACTIONS |
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US20020119890A1 (en) * | 2000-12-04 | 2002-08-29 | Wenzel Timothy T. | Catalyst preparation method |
US20050159300A1 (en) * | 2004-01-21 | 2005-07-21 | Jensen Michael D. | Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength |
JP2015113282A (ja) * | 2013-12-09 | 2015-06-22 | 広栄化学工業株式会社 | ハフニウム化合物とジルコニウム化合物の混合組成物およびその製造方法 |
US20160362510A1 (en) * | 2014-02-11 | 2016-12-15 | Univation Technologies, Llc | Method to prepare ethylene copolymers |
WO2019027585A1 (en) * | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | MIXED CATALYSTS COMPRISING UNDRAWNED HAFNOCENES WITH -CH2-SIME3 FRACTIONS |
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