CA3128864A1 - Polyethylene having high degree of crosslinking and crosslinked polyethylene pipe comprising the same - Google Patents
Polyethylene having high degree of crosslinking and crosslinked polyethylene pipe comprising the same Download PDFInfo
- Publication number
- CA3128864A1 CA3128864A1 CA3128864A CA3128864A CA3128864A1 CA 3128864 A1 CA3128864 A1 CA 3128864A1 CA 3128864 A CA3128864 A CA 3128864A CA 3128864 A CA3128864 A CA 3128864A CA 3128864 A1 CA3128864 A1 CA 3128864A1
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- CA
- Canada
- Prior art keywords
- group
- polyethylene
- chemical formula
- crosslinking
- date received
- Prior art date
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- Pending
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- -1 Polyethylene Polymers 0.000 title claims abstract description 144
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 83
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 83
- 238000004132 cross linking Methods 0.000 title claims abstract description 60
- 239000004703 cross-linked polyethylene Substances 0.000 title claims abstract description 34
- 229920003020 cross-linked polyethylene Polymers 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 claims description 69
- 150000001875 compounds Chemical class 0.000 claims description 65
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 17
- 150000002367 halogens Chemical class 0.000 claims description 17
- 230000010354 integration Effects 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 239000012968 metallocene catalyst Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000004717 peroxide crosslinked polyethylene Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 7
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Chemical group 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001923 cyclic compounds Chemical class 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 229910052732 germanium Chemical group 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims 1
- 230000001965 increasing effect Effects 0.000 abstract description 8
- 230000001747 exhibiting effect Effects 0.000 abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- 239000000460 chlorine Substances 0.000 description 25
- 239000000243 solution Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001125 extrusion Methods 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 229920001903 high density polyethylene Polymers 0.000 description 10
- 239000004700 high-density polyethylene Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- RXXXUIOZOITBII-UHFFFAOYSA-N indeno[1,2-g]indole Chemical class C1=C2C=CC=CC2=C2C1=C1N=CC=C1C=C2 RXXXUIOZOITBII-UHFFFAOYSA-N 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 229920013716 polyethylene resin Polymers 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 101150041968 CDC13 gene Proteins 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000004719 irradiation crosslinked polyethylene Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000004718 silane crosslinked polyethylene Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910003828 SiH3 Inorganic materials 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000005103 alkyl silyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000005131 dialkylammonium group Chemical group 0.000 description 2
- WFZSIVNWLIYDJZ-UHFFFAOYSA-N dichloro-methyl-[6-[(2-methylpropan-2-yl)oxy]hexyl]silane Chemical compound CC(C)(C)OCCCCCC[Si](C)(Cl)Cl WFZSIVNWLIYDJZ-UHFFFAOYSA-N 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000004073 vulcanization Methods 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
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- NOSXUFXBUISMPR-UHFFFAOYSA-N 1-tert-butylperoxyhexane Chemical compound CCCCCCOOC(C)(C)C NOSXUFXBUISMPR-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 241000985630 Lota lota Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 244000126002 Ziziphus vulgaris Species 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000002933 cyclohexyloxy group Chemical group C1(CCCCC1)O* 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000006229 isopropoxyethyl group Chemical group [H]C([H])([H])C([H])(OC([H])([H])C([H])([H])*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- KUFYUMSBZMUWAN-UHFFFAOYSA-N n-methyl-n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCC KUFYUMSBZMUWAN-UHFFFAOYSA-N 0.000 description 1
- HSUGDXPUFCVGES-UHFFFAOYSA-N n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCNCCCCCCCCCCCCCC HSUGDXPUFCVGES-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
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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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- C08F4/65904—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with another component of C08F4/64
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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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- C08F4/65922—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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- 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
- C08F4/62—Refractory metals or compounds thereof
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- 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
- C08F4/65927—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 bridged
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2420/00—Metallocene catalysts
- C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom
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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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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
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Abstract
The present invention relates to polyethylene having a high degree of cross-linking, and a cross-linked polyethylene pipe comprising the same. The polyethylene according to the present invention has an ultra-high molecular weight so as to have increased cross-linking speed, thereby exhibiting a sufficient degree of cross-linking even when cross-linking time is short, and thus can exhibit excellent strength and pressure resistance.
Description
TITLE OF THE INVENTION
POLYETHYLENE HAVING HIGH DEGREE OF CROSSLINKING
AND CROSSLINKED POLYETHYLENE PIPE COMPRISING THE
SAME
CROSS-REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of Korean Patent Application No. 10-2019-0020025 filed on February 20, 2019 and Korean Patent Application No. 10-2020-0020644 filed on February 19, 2020 with the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.
Field of the Invention The present disclosure relates to a polyethylene having high degree of crosslinking and a crosslinked polyethylene pipe comprising the same.
Description of the Related Art Crosslinked polyethylene was developed by an electric wire company in 1960 to improve the temperature characteristics by heat generation of an electric wire, and German Thomas Engel has produced a pipe having excellent durability using this polyethylene in 1967.
The crosslinked polyethylene is one that is modified into polyethylene having a three-dimensional network structure by Date Recue/Date Received 2021-08-03 crosslinking high density polyethylene (HDPE) having a linear molecular structure, and has excellent characteristics such as heat resistance, durability, chemical resistance, and flexibility.
On the other hand, as the method of crosslinking polyethylene in this way, there may be mentioned a crosslinking method using an organic peroxide (peroxide crosslinking), a crosslinking method using a silane compound (silane crosslinking), and a crosslinking method using an electron beam irradiation (radiation crosslinking).
In general, polyethylene crosslinked by organic peroxide is referred to as PE-Xa, polyethylene crosslinked by a silane compound is referred to as PE-Xb, and polyethylene crosslinked by an electron beam irradiation is referred to as PE-Xc.
In the case of PE-Xa, it has superior physical properties compared to PE-Xb and PE-Xc, and can produce flexible pipe products, but has a disadvantage that the production output (linear velocity) is low.
Therefore, if the linear velocity is increased in order to increase the production output, the residence time in the extruder is reduced, and the time during which the resin containing the crosslinking agent is exposed to heat, that is, the crosslinking time is shortened, and thus, there is a problem that the degree of crosslinking decreases.
Accordingly, there is a need to develop a crosslinked polyethylene pipe having a higher degree of crosslinking while increasing the production output.
POLYETHYLENE HAVING HIGH DEGREE OF CROSSLINKING
AND CROSSLINKED POLYETHYLENE PIPE COMPRISING THE
SAME
CROSS-REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of Korean Patent Application No. 10-2019-0020025 filed on February 20, 2019 and Korean Patent Application No. 10-2020-0020644 filed on February 19, 2020 with the Korean Intellectual Property Office, the disclosures of which are incorporated herein by reference in their entirety.
Field of the Invention The present disclosure relates to a polyethylene having high degree of crosslinking and a crosslinked polyethylene pipe comprising the same.
Description of the Related Art Crosslinked polyethylene was developed by an electric wire company in 1960 to improve the temperature characteristics by heat generation of an electric wire, and German Thomas Engel has produced a pipe having excellent durability using this polyethylene in 1967.
The crosslinked polyethylene is one that is modified into polyethylene having a three-dimensional network structure by Date Recue/Date Received 2021-08-03 crosslinking high density polyethylene (HDPE) having a linear molecular structure, and has excellent characteristics such as heat resistance, durability, chemical resistance, and flexibility.
On the other hand, as the method of crosslinking polyethylene in this way, there may be mentioned a crosslinking method using an organic peroxide (peroxide crosslinking), a crosslinking method using a silane compound (silane crosslinking), and a crosslinking method using an electron beam irradiation (radiation crosslinking).
In general, polyethylene crosslinked by organic peroxide is referred to as PE-Xa, polyethylene crosslinked by a silane compound is referred to as PE-Xb, and polyethylene crosslinked by an electron beam irradiation is referred to as PE-Xc.
In the case of PE-Xa, it has superior physical properties compared to PE-Xb and PE-Xc, and can produce flexible pipe products, but has a disadvantage that the production output (linear velocity) is low.
Therefore, if the linear velocity is increased in order to increase the production output, the residence time in the extruder is reduced, and the time during which the resin containing the crosslinking agent is exposed to heat, that is, the crosslinking time is shortened, and thus, there is a problem that the degree of crosslinking decreases.
Accordingly, there is a need to develop a crosslinked polyethylene pipe having a higher degree of crosslinking while increasing the production output.
2 Date Recue/Date Received 2021-08-03 SUMMARY OF THE INVENTION
[Technical Problem]
Therefore, the present disclosure has been made in view of the above-mentioned problems, and the object of the present disclosure is to provide polyethylene exhibiting a high degree of crosslinking even when a short crosslinking time is applied to improve productivity, and thus has excellent physical properties, and a crosslinked polyethylene pipe comprising the same.
[Technical Solution]
In order to achieve that above object, according to one embodiment of the present disclosure, there is provided a polyethylene which satisfies:
a density of 0.940 g/cm3 or more and 0.960 g/cm3 or less as measured according to ASTM D792;
a number average molecular weight (Mn) of 20,000 g/mol or more and 70,000 g/mol or less;
a weight average molecular weight (Mw) of 150,000 g/mol or more and 350,000 g/mol or less;
a melt index (MI21.6) of 1 g/10min or more and 10 g/10min or less as measured at a temperature of 190 C under a load of 21.6 kg according to ASTM D1238, and an integration value in a region where log Mw value is 6.0 or more, of 4.5% or more relative to the total integration value, in a
[Technical Problem]
Therefore, the present disclosure has been made in view of the above-mentioned problems, and the object of the present disclosure is to provide polyethylene exhibiting a high degree of crosslinking even when a short crosslinking time is applied to improve productivity, and thus has excellent physical properties, and a crosslinked polyethylene pipe comprising the same.
[Technical Solution]
In order to achieve that above object, according to one embodiment of the present disclosure, there is provided a polyethylene which satisfies:
a density of 0.940 g/cm3 or more and 0.960 g/cm3 or less as measured according to ASTM D792;
a number average molecular weight (Mn) of 20,000 g/mol or more and 70,000 g/mol or less;
a weight average molecular weight (Mw) of 150,000 g/mol or more and 350,000 g/mol or less;
a melt index (MI21.6) of 1 g/10min or more and 10 g/10min or less as measured at a temperature of 190 C under a load of 21.6 kg according to ASTM D1238, and an integration value in a region where log Mw value is 6.0 or more, of 4.5% or more relative to the total integration value, in a
3 Date Recue/Date Received 2021-08-03 GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw.
According to another embodiment of the present disclosure, there is provided a crosslinked polyethylene pipe including the polyethylene.
[Advantageous Effects]
The polyethylene according to the present disclosure has a high content of ultra-high molecular weight and thus improves the crosslinking rate (T90), and even if the linear velocity is increased and the crosslinking time is shortened to increase productivity, it can exhibit a sufficient degree of crosslinking of 70% or more, thereby exhibiting excellent strength and pressure resistance characteristics.
Therefore, it can be usefully used in the production of crosslinked polyethylene pipes, especially PE-Xa pipes.
DETAILED DESCRIPTION OF THE EMBODIMENTS
As used herein, terms such as first, second, and the like may be used to describe various components, and the terms are used only to discriminate one component from another component.
Also, the terms used herein are used only to describe exemplary embodiments, and are not intended to limit the present disclosure. A singular expression includes a plural expression unless they have definitely opposite meanings in the context. It should be understood that the terms "comprise", "include", and
According to another embodiment of the present disclosure, there is provided a crosslinked polyethylene pipe including the polyethylene.
[Advantageous Effects]
The polyethylene according to the present disclosure has a high content of ultra-high molecular weight and thus improves the crosslinking rate (T90), and even if the linear velocity is increased and the crosslinking time is shortened to increase productivity, it can exhibit a sufficient degree of crosslinking of 70% or more, thereby exhibiting excellent strength and pressure resistance characteristics.
Therefore, it can be usefully used in the production of crosslinked polyethylene pipes, especially PE-Xa pipes.
DETAILED DESCRIPTION OF THE EMBODIMENTS
As used herein, terms such as first, second, and the like may be used to describe various components, and the terms are used only to discriminate one component from another component.
Also, the terms used herein are used only to describe exemplary embodiments, and are not intended to limit the present disclosure. A singular expression includes a plural expression unless they have definitely opposite meanings in the context. It should be understood that the terms "comprise", "include", and
4 Date Recue/Date Received 2021-08-03 "have" as used herein are intended to designate the presence of stated features, steps, constitutional elements, or combinations thereof, but it should be understood that they do not preclude a possibility of existence or addition of one or more other features, steps, constitutional elements, or combinations thereof.
Since the present disclosure may be modified in various forms and may have several embodiments, particular embodiments will be illustrated and described in detail below. However, it will be understood that the present disclosure is not limited to the particular embodiments but the invention includes all modifications, equivalents, and alternatives falling within the scope and sprit of the present disclosure.
Hereinafter, the polyethylene of the present disclosure and a crosslinked polyethylene pipe comprising the same will be described in more detail.
The polyethylene according to one embodiment of the present disclosure is characterized in that a density measured according to ASTM D792 is 0.940 g/cm3 or more and 0.960 g/cm3 or less; a number average molecular weight (Mn) is 20,000 g/mol or more and 70,000 g/mol or less; a melt index (MI21.6) is 1 g/10min or more and 10 g/10min or less as measured at a temperature of 190 C under a load of 21.6 kg according to ASTM D1238; and an integration value in a region where log Mw value is 6.0 or more, of 4.5% or more relative to the total integration value, in a GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw.
Since the present disclosure may be modified in various forms and may have several embodiments, particular embodiments will be illustrated and described in detail below. However, it will be understood that the present disclosure is not limited to the particular embodiments but the invention includes all modifications, equivalents, and alternatives falling within the scope and sprit of the present disclosure.
Hereinafter, the polyethylene of the present disclosure and a crosslinked polyethylene pipe comprising the same will be described in more detail.
The polyethylene according to one embodiment of the present disclosure is characterized in that a density measured according to ASTM D792 is 0.940 g/cm3 or more and 0.960 g/cm3 or less; a number average molecular weight (Mn) is 20,000 g/mol or more and 70,000 g/mol or less; a melt index (MI21.6) is 1 g/10min or more and 10 g/10min or less as measured at a temperature of 190 C under a load of 21.6 kg according to ASTM D1238; and an integration value in a region where log Mw value is 6.0 or more, of 4.5% or more relative to the total integration value, in a GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw.
5 Date Recue/Date Received 2021-08-03 The crosslinked polyethylene is one that is modified into polyethylene having a three-dimensional network structure by crosslinking high density polyethylene (HDPE) having a linear molecular structure, and has excellent characteristics such as heat resistance, durability, chemical resistance, and flexibility.
Pipes produced from such crosslinked polyethylene are usually produced by mixing polyethylene with a crosslinking agent and an antioxidant and then extrusion-molding the mixture with a RAM type extruder.
Among the pipes produced from the crosslinked polyethylene in this way, PE-Xa has superior crosslinking physical properties compared to PE-Xb and PE-Xc, and can produce flexible pipe products, but has a disadvantage that the productivity is low.
In this regard, if the linear velocity of the extruder is increased in order to increase productivity, the residence time in the extruder is shortened, so that the crosslinking reaction time between the polyethylene resin and the crosslinking agent is shortened, and so the degree of crosslinking is lowered.
Therefore, the present disclosure has been designed to overcome the low productivity that is a disadvantage of PE-Xa pipes, and the inventors have developed a polyethylene resin suitable for use in PE-Xa pipes in which the molecular structure of polyethylene has been improved, and despite the shorter crosslinking time than before, the crosslinking rate and degree of crosslinking are not reduced and are maintained at 70% or more.
Pipes produced from such crosslinked polyethylene are usually produced by mixing polyethylene with a crosslinking agent and an antioxidant and then extrusion-molding the mixture with a RAM type extruder.
Among the pipes produced from the crosslinked polyethylene in this way, PE-Xa has superior crosslinking physical properties compared to PE-Xb and PE-Xc, and can produce flexible pipe products, but has a disadvantage that the productivity is low.
In this regard, if the linear velocity of the extruder is increased in order to increase productivity, the residence time in the extruder is shortened, so that the crosslinking reaction time between the polyethylene resin and the crosslinking agent is shortened, and so the degree of crosslinking is lowered.
Therefore, the present disclosure has been designed to overcome the low productivity that is a disadvantage of PE-Xa pipes, and the inventors have developed a polyethylene resin suitable for use in PE-Xa pipes in which the molecular structure of polyethylene has been improved, and despite the shorter crosslinking time than before, the crosslinking rate and degree of crosslinking are not reduced and are maintained at 70% or more.
6 Date Recue/Date Received 2021-08-03 More specifically, paying attention to the fact that the crosslinking rate of the polyethylene resin and the crosslinking agent increases as the content of the polymer in the resin increases, a faster crosslinking rate (T90) can be achieved by increasing the ultra-high molecular weight (polymer with Log Mw 6.0 or more) compared to polyethylene with the same level of melt index, whereby even if the linear velocity of the extruder is increased compared to a conventional method, the degree of crosslinking is maintained at 70%
or more, and thus, the effect of improving productivity can be achieved.
Specifically, the polyethylene according to an embodiment of the present disclosure may be high density polyethylene (HDPE) having a density of 0.940 g/cm3 or more and 0.960 g/cm3 or less as measured according to ASTM D792.
More specifically, according to one embodiment, the density of the polyethylene of the present disclosure may be 0.940 g/cm3 or more, or 0.942 g/cm3 or more, or 0.945 g/cm3 or more, or 0.947 g/cm3 or more, and 0.960 g/cm3 or less, or 0.958 g/cm3 or less, or 0.957 g/cm3 or less, or 0.956 g/cm3 or less. By having the density range as described above, the polyethylene of the present disclosure can satisfy excellent pressure resistance characteristics.
Further, the polyethylene according to an embodiment of the present disclosure has a number average molecular weight (Mn) of 20,000 to 70,000 g/mol. More specifically, the number average molecular weight may be 20,000 g/mol or more, or 25,000 g/mol or
or more, and thus, the effect of improving productivity can be achieved.
Specifically, the polyethylene according to an embodiment of the present disclosure may be high density polyethylene (HDPE) having a density of 0.940 g/cm3 or more and 0.960 g/cm3 or less as measured according to ASTM D792.
More specifically, according to one embodiment, the density of the polyethylene of the present disclosure may be 0.940 g/cm3 or more, or 0.942 g/cm3 or more, or 0.945 g/cm3 or more, or 0.947 g/cm3 or more, and 0.960 g/cm3 or less, or 0.958 g/cm3 or less, or 0.957 g/cm3 or less, or 0.956 g/cm3 or less. By having the density range as described above, the polyethylene of the present disclosure can satisfy excellent pressure resistance characteristics.
Further, the polyethylene according to an embodiment of the present disclosure has a number average molecular weight (Mn) of 20,000 to 70,000 g/mol. More specifically, the number average molecular weight may be 20,000 g/mol or more, or 25,000 g/mol or
7 Date Recue/Date Received 2021-08-03 more, or 30,000 g/mol or more, and 70,000 g/mol or less, or 60,000 g/mol or less, or 55,000 g/mol or less.
Further, the polyethylene according to an embodiment of the present disclosure has a weight average molecular weight (Mw) of 150,000 to 350,000 g/mol. More specifically, the weight average molecular weight may be 150,000 g/mol or more, or 180,000 g/mol or more, or 200,000 g/mol or more, and 350,000 g/mol or less, or 340,000 g/mol or less, or 330,000 g/mol or less, or 320,000 g/mol or less.
By having the range of the number average molecular weight (Mn) and the weight average molecular weight (Mw) as described above, the polyethylene of the present disclosure may exhibit improved crosslinking properties.
Further, the polyethylene according to an embodiment of the present disclosure has a molecular weight distribution (MWD, Mw/Mn) of 3.0 to 10Ø More specifically, the molecular weight distribution may be 3.0 or more, or 3.5 or more, or 4.0 or more, or 4.5 or more, and 10.0 or less, or 9.0 or less, or 8.5 or less.
By having the molecular weight distribution as described above, the polyethylene of the present disclosure can satisfy high crosslinking properties.
In the present disclosure, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution are measured in which the weight average molecular weight (Mw) and the number average molecular
Further, the polyethylene according to an embodiment of the present disclosure has a weight average molecular weight (Mw) of 150,000 to 350,000 g/mol. More specifically, the weight average molecular weight may be 150,000 g/mol or more, or 180,000 g/mol or more, or 200,000 g/mol or more, and 350,000 g/mol or less, or 340,000 g/mol or less, or 330,000 g/mol or less, or 320,000 g/mol or less.
By having the range of the number average molecular weight (Mn) and the weight average molecular weight (Mw) as described above, the polyethylene of the present disclosure may exhibit improved crosslinking properties.
Further, the polyethylene according to an embodiment of the present disclosure has a molecular weight distribution (MWD, Mw/Mn) of 3.0 to 10Ø More specifically, the molecular weight distribution may be 3.0 or more, or 3.5 or more, or 4.0 or more, or 4.5 or more, and 10.0 or less, or 9.0 or less, or 8.5 or less.
By having the molecular weight distribution as described above, the polyethylene of the present disclosure can satisfy high crosslinking properties.
In the present disclosure, the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution are measured in which the weight average molecular weight (Mw) and the number average molecular
8 Date Recue/Date Received 2021-08-03 weight (Mn) of polyethylene are respectively measured using gel permeation chromatography (GPC), and the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) was calculated as the polydispersity index.
Specifically, a polyethylene sample was evaluated using a Waters PL-GPC220 instrument using a PLgel Mixed-B column (300 mm in length) from Polymer Laboratories, wherein an evaluation temperature is set to 160 C, 1,2,4-trichlorobenzene is used as a solvent, and a flow rate is set to 1 mL/min. In addition, a sample is prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 pL. A calibration curve formed by using a polystyrene standard is used to determine Mw and Mn values. The molecular weight of the polystyrene standard used was nine types of 2,000 /
10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
Further, the polyethylene according to an embodiment of the present disclosure has a melt index (MI21.6) of 1 to 10 g/10min as measured at a temperature of 190 C under a load of 21.6 kg according to the ASTM D1238 standard. More specifically, the melt index (MI21.6) may be 1 g/10min or more, or 1.2 g/10min or more, or 1.4 g/10min or more, and 10 g/10min or less, or 7.5 g/10min or less, or 5 g/10min or less.
By having the range of the melt index (MI21.6) as described above, the polyethylene of the present disclosure can satisfy high crosslinking characteristics.
Specifically, a polyethylene sample was evaluated using a Waters PL-GPC220 instrument using a PLgel Mixed-B column (300 mm in length) from Polymer Laboratories, wherein an evaluation temperature is set to 160 C, 1,2,4-trichlorobenzene is used as a solvent, and a flow rate is set to 1 mL/min. In addition, a sample is prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 pL. A calibration curve formed by using a polystyrene standard is used to determine Mw and Mn values. The molecular weight of the polystyrene standard used was nine types of 2,000 /
10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
Further, the polyethylene according to an embodiment of the present disclosure has a melt index (MI21.6) of 1 to 10 g/10min as measured at a temperature of 190 C under a load of 21.6 kg according to the ASTM D1238 standard. More specifically, the melt index (MI21.6) may be 1 g/10min or more, or 1.2 g/10min or more, or 1.4 g/10min or more, and 10 g/10min or less, or 7.5 g/10min or less, or 5 g/10min or less.
By having the range of the melt index (MI21.6) as described above, the polyethylene of the present disclosure can satisfy high crosslinking characteristics.
9 Date Recue/Date Received 2021-08-03 Further, the polyethylene according to an embodiment of the present disclosure may have an integration value in a region where log Mw value is 6.0 or less, of 4.5% or more relative to the total integration value, in a GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw. The GPC curve graph means that the logarithmic function molecular weight and mass fraction of polyethylene are measured by GPC and plotted on the x and y axes.
Further, in the above, Mw means a weight-average molecular weight.
More specifically, according to an embodiment, the polyethylene of the present disclosure may have the integration value in a region where the Log Mw value is 6.0 or more, of 4.5% or more, or 4.7% or more, or 5% or more, or 5.2% or more, or 5.5% or more, or 6.0% or more, and 10% or less, or 9% or less, or 8.5% or less, or 8.0% or less, or 7.7% or less of the total integration value.
As described above, the integral value of the region where the Log Mw value is 6.0 or more being 4.5% or more means that the polyethylene of the present disclosure has a high molecular weight content. This improves the crosslinking rate, which is proportional to the content of the polymer in the polyethylene resin, the polyethylene of the present disclosure can achieve a higher degree of crosslinking within the same time during a crosslinking reaction with a crosslinking agent.
Therefore, when the crosslinked polyethylene is prepared using the polyethylene of the present disclosure, even when comparing with polyethylene having the same level of melt index, Date Recue/Date Received 2021-08-03 and increasing the linear velocity of the extruder than that of a conventional method, the degree of crosslinking is maintained at 70%
or more, thereby achieving an effect of improving productivity without deteriorating physical properties.
Further, when the crosslinked polyethylene is prepared using the polyethylene of the present disclosure, the crosslinking rate (T90) measured according to ASTM D 5289 shows a fast crosslinking rate of 10 minutes or less. More specifically, the crosslinking rate (T90) may be 10 minutes or less, or 9.8 minutes or less, or 9.5 minutes or less, or 9.0 minutes or less, and 5 minutes or more, or 6 minutes or more, or 7 minutes or more.
On the other hand, polyethylene according to an embodiment of the present disclosure having the physical properties as described can be prepared by a preparation method comprising polymerizing an ethylene monomer in the presence of a specific metallocene compound as a catalytically active component.
More specifically, the polyethylene of the present disclosure includes, but not limited thereto, a first metallocene compound represented by the following Chemical Formula 1; and a second metallocene compound represented by the following Chemical Formula 3, and can be prepared by polymerizing an ethylene monomer in the presence of a hybrid metallocene catalyst in which a molar ratio between the first metallocene compound and the second metallocene compound is 20:1 to 5:1.
[Chemical Formula 1]
Date Recue/Date Received 2021-08-03 Cl Qi \\*
/*/MI
in the Chemical Formula 1, Qi and Q2 are the same as or different from each other, and each independently represents hydrogen, a halogen, a Cl to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
B is carbon, silicon, or germanium;
Mi is a Group 4 transition metal;
Xi and X2 are the same as or different from each other, and each independently represents a halogen, a Cl to C20 alkyl group, a C2 to C10 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
one of Ci and C2 is represented by the following Chemical Formula 2a or Chemical Formula 2b, and the other of Ci and C2 is represented by the following Chemical Formula 2c;
[Chemical Formula 2a]
Date Recue/Date Received 2021-08-03 [Chemical Formula 2b]
R2' Rs' R8' R8' R5' Ric; RI21 R11' [Chemical Formula 2c]
R20 O.* R15 in the Chemical Formulas 2a, 2b and 2c, Ri to R21 and Ri' to R13' are the same as or different from each other, and each independently represents hydrogen, a halogen, Date Recue/Date Received 2021-08-03 a Cl to C20 alkyl group, a Cl to C20 haloalkyl group, a C2 to C20 alkenyl group, a Cl to C20 alkylsilyl group, a Cl to C20 silylalkyl group, a Cl to C20 alkoxysilyl group, a Cl to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, provided that at least one of R9 to R13 and R9' to R13' is a Cl to C20 haloalkyl group, [Chemical Formula 3]
Cpe'r- 'X4 in the Chemical Formula 3, M2 is a Group 4 transition metal;
Cpi and Cp2 are the same as or different from each other, and each independently represents any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-l-indenyl and fluorenyl, one or more hydrogens of the cyclic group may be each independently substituted with any one substituent selected among a Cl to 20 alkyl, a Cl to C20 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl; and X3 and X4 are the same as or different from each other, and each independently represents a halogen, a Cl to C20 alkyl, a C2 to C10 alkenyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl.
The substituents of Chemical Formulas 1 and 2 will be described in more detail below.
Date Recue/Date Received 2021-08-03 The Cl to C20 alkyl group includes a linear or branched alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like may be mentioned, but is not limited thereto.
The C2 to C20 alkenyl group includes a linear or branched alkenyl group, and specifically, an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like may be mentioned, but is not limited thereto.
The C6 to C20 aryl group includes a monocyclic or condensed ring aryl group, and specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like may be mentioned, but is not limited thereto.
The Cl to C20 alkoxy group may include, but not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.
The C2 to C20 alkoxyalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with an alkoxy group, and specifically, alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group and a tert-butoxyhexyl group; or aryloxyalkyl groups such as a phenoxyhexyl group may be mentioned, but is not limited thereto.
Date Recue/Date Received 2021-08-03 The Cl to C20 alkylsilyl group or the Cl to C20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH3 are substituted with 1 to 3 alkyl or alkoxy groups as described above, and specifically, alkylsilyl groups such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, or a dimethylpropylsilyl group; alkoxysilyl groups such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group or a dimethoxyethoxysilyl group; alkoxyalkylsilyl groups such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group may be mentioned, but is not limited thereto.
The Cl to C20 silylalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with a silyl group, and specifically, -CH2-SiH3, a methylsilylmethyl group, or a dimethylethoxysilylpropyl group may be mentioned, but are not limited thereto.
The halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
The above-described substituents may be optionally substituted with one or more substituents selected from the group consisting of a hydroxy group; a halogen; an alkyl group or an alkenyl group, an aryl group, an alkoxy group; an alkyl or an alkenyl group, an aryl group, or an alkoxy group including at least one heteroatom selected among the heteroatoms of Groups 14 to 16; a silyl group; an alkylsilyl group or an alkoxysilyl group; a phosphine Date Recue/Date Received 2021-08-03 group; a phosphide group; a sulfonate group; and a sulfone group which are within a range exhibiting the same or similar effect as the desired effect.
The Group 4 transition metal may include titanium (Ti), zirconium (Zr), and hafnium (Hf), but are not limited thereto.
According to an embodiment of the present disclosure, Ri to R21 and Ri' to R13' in Chemical Formulas 2a, 2b, and 2c may be each independently hydrogen, a halogen, a Cl to C20 alkyl group, or a Cl to C20 haloalkyl group, and at least one of R9 to R13 and R9' to R13' may be a Cl to C20 haloalkyl group.
More specifically, Ri to R21 and Ri' to Ri3' may be each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a fluoroalkyl group, and at least one of R9 to R13 and R9' to Ri3' may be fluoroalkyl, but is not limited thereto.
According to an embodiment of the present disclosure Qi and Q2 in Chemical Formula 1 may be each independently hydrogen, a halogen, a Cl to C20 alkyl group, or a C2 to C20 alkoxyalkyl group.
More specifically, Qi and Q2 may be each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, a tert-butoxymethyl group, a tert-butoxyhexyl group, 1-ethoxyethyl group, 1-methyl-l-methoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group, but are not Date Recue/Date Received 2021-08-03 limited thereto.
According to an embodiment of the present disclosure, B in Chemical Formula 1 is preferably silicon, but is not limited thereto.
According to an embodiment of the present disclosure, Xi and X2 in Chemical Formula 1 may be each independently a halogen or a C1 to C20 alkyl group.
The first metallocene compound of Chemical Formula 1 forms a structure in which an indeno-indole derivative and a cyclopentadiene derivative are asymmetrically crosslinked by a bridge, and by having a non-shared electron pair capable of functioning as a Lewis base in the ligand structure, it is supported on the surface having Lewis acid properties of the support, and exhibits high polymerization activity even when supported. Further, by including the electronically rich indeno-indole group and cyclopentadiene group, the activity is high, and excellent copolymerization property and high activity are maintained due to appropriate steric hindrance and the electronic effect of the ligand.
Moreover, beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno-indole derivative grows can be stabilized by hydrogen bonding to suppress beta-hydrogen elimination and polymerize an ultra-high molecular weight polyolefin.
In particular, one or more of R9 to Ri3 and R9' to R13' in the transition metal compound of Chemical Formula 1 includes a C1-C20 haloalkyl group. Further, haloalkyl groups containing halogen elements other than other fluorine may also interact with beta-Date Recue/Date Received 2021-08-03 hydrogen, but hydrogen forms a hydrogen bond with highly electronegative atoms such as nitrogen, oxygen, and fluorine. All haloalkyl groups do not form a hydrogen bond with beta-H. It does not form a hydrogen bond with beta-H by including a haloalkyl group, but is an effect exhibited by introducing a fluorine substituent. For example, a fluoroalkyl group, that is, CF3, etc. may be mentioned. It acts like the nitrogen atom of the indeno-indole derivative, stabilizes beta-hydrogen of a growing polymer chain by hydrogen bonding, further suppresses beta-hydrogen elimination, and more effectively can achieve the polymerization of the ultra-high molecular weight polyolefin. In other words, it maintains the basic skeleton of the catalyst in which the indeno-indole derivative and the cyclopentadiene derivative are asymmetrically crosslinked by a bridge, and by introducing substituents such as CF3 which is a stronger hydrogen bond acceptor, beta-hydrogen is stabilized by hydrogen bonding, thereby enhancing the effect of suppressing beta-hydrogen elimination and enabling the polymerization of ultra-high molecular weight polyolefin.
According to an embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 2a may include a compound represented by the following structural formula, but the present disclosure is not limited thereto.
Date Recue/Date Received 2021-08-03 0 r.
0.
According to an embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 2b may be a compound represented by the following structural formula, but the present disclosure is not limited thereto.
According to an embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 2c may include a compound represented by one of the following structural formulas, but the present disclosure is not limited thereto.
=
Date Recue/Date Received 2021-08-03 Oa* d<
--,--' According to an embodiment of the present disclosure, specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by Chemical Formula 1-1, but the present disclosure is not limited thereto.
[Structural Formula 1-1]
F3o ,.:-._:-----\
N
Si' ZrCl2 >
,/ 0(-1 ...
'-'7\/0 The first metallocene compound may be synthesized by applying known reactions, and for a more detailed synthesis method, please refer to Examples.
According to an embodiment of the present disclosure, Cpi and Cp2 in Chemical Formula 3 may be each independently cyclopentadienyl or indenyl, and at least one hydrogen of the cyclopentadienyl or indenyl may be each independently substituted Date Recue/Date Received 2021-08-03 with any one substituent selected among a Cl to 20 alkyl or a C2 to C20 alkoxyalkyl.
According to an embodiment of the present disclosure, M2 in Chemical Formula 3 is preferably zirconium (Zr), but the present disclosure is not limited thereto.
According to an embodiment of the present disclosure, X3 and X4 in Chemical Formula 3 may be each independently a halogen or a Cl to C20 alkyl group.
The second metallocene compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but the present disclosure is not limited thereto.
)1/4sCt-412 .aca2 ro Zrd2 \rCl2 >Lo LO
C)Ctieli rCl2 Date Recue/Date Received 2021-08-03 ' 4.40-1,3L_C ZrC' jZiC 12 ZoCl2 Ci" ( = 4041I
'ZrC12 Further, the second metallocene compound represented by Chemical Formula 3 may be more preferably represented by the following Formula 3-1:
[Chemical Formula 3-1]
>r ZrC42 )%0PSØ-Nir's\AsS
The second metallocene compound represented by Chemical Formula 3 may be synthesized by applying known reactions, and for a more detailed synthesis method, refer to Examples.
In the hybrid metallocene catalyst according to an embodiment of the present disclosure, the first metallocene compound represented by Chemical Formula 1 can mainly contribute to the Date Recue/Date Received 2021-08-03 expression of high molecular weight polyethylene, and the second metallocene compound represented by Chemical Formula 3 can mainly contribute to the expression of low molecular weight polyethylene with a narrow molecular weight distribution.
As the hybrid metallocene catalyst according to an embodiment of the present disclosure uses as a hybrid metallocene catalyst using a metallocene compound with a low molecular weight expression having a narrow polydispersity index and a metallocene compound with a high molecular weight expression together, it is advantageous for polymerizing the polyethylene of the present disclosure described above.
In the hybrid metallocene catalyst of the present disclosure, the molar ratio between the first metallocene compound represented by Chemical Formula 1 and the second metallocene compound represented by Chemical Formula 3 may be 20:1 to 5:1, or 18:1 to 7:1, or 15:1 to 8:1. At this time, when the molar ratio of the first and second metallocene compounds exceeds 20:1 and the content of the first metallocene compound is too large, the density is reduced and the pipe pressure resistance can be deteriorated. When the molar ratio is less than 5: 1 and the content of the first metallocene compound is too small, the crosslinking rate can become slow.
Therefore, from such a viewpoint, the molar ratio of the first and second metallocene compounds may be preferably in the above-described range.
In the hybrid metallocene catalyst used in the present Date Recue/Date Received 2021-08-03 disclosure, one or more of the first metallocene compound represented by Chemical Formula 1 and one or more of the second metallocene compound represented by Chemical Formula 3 may be supported on respective supports together with a cocatalyst compound.
In the hybrid metallocene catalyst of the present disclosure, the cocatalyst supported together on the support for activating the first and second metallocene compounds is an organometallic compound containing a Group 13 metal, and it is not particularly limited as long as it can be used when polymerizing olefins under a general metallocene catalyst.
Specifically, the cocatalyst compound may include at least one selected among an aluminum-containing first cocatalyst of the following Chemical Formula 4 and a borate-based second cocatalyst of the following Chemical Formula 5.
[Chemical Formula 4]
-[Al(Ra)-0]k-in the Chemical Formula 4, each Ra is independently a halogen, a halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more, [Chemical Formula 5]
T[BG4]-in the Chemical Formula 5, T+ is a +1 charge polyatomic ion, B
is boron in an oxidation state of +3, each G is independently selected from the group consisting of a hydride group, a dialkylamido group, a Date Recue/Date Received 2021-08-03 halide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, wherein the G has 20 or less carbon atoms, provided that G is a halide at one or less position.
By using the first and second cocatalysts as described above, the polymerization activity can be further enhanced.
The first cocatalyst of Chemical Formula 4 may be an alkylaluminoxane-based compound wherein the repeating units are combined into a linear, circular, or network form. Specific examples of the first cocatalyst include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.
Further, the second cocatalyst of Chemical Formula 5 may be a trisubstituted ammonium salt, a dialkylammonium salt, or a trisubstituted phosphate type of borate compound. Specific examples of the second cocatalyst include a borate-based compound in the form of a trisubstituted ammonium salt, such as trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium Date Recue/Date Received 2021-08-03 tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N, N-dimethylanilin ium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N, N-dimethyl(2,4,6-trimethylanilinium )tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate and the like; a borate-based compound in the form of a dialkylammonium salt, such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl) borate or dicyclohexylammonium tetrakis(pentafluorophenyl)borate; or a borate-based compound in the form of a trisubstituted phosphonium salt, such as triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, or Date Recue/Date Received 2021-08-03 tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.
In the metallocene catalyst according to the present disclosure, the mass ratio of the total weight of the transition metals contained in the first and second metallocene compounds relative to the support may be 1 : 10 to 1 : 1,000. When the support and the metallocene compound are contained in the range of the above mass ratio, an optimal shape can be provided. Further, the mass ratio of the cocatalyst compound to the support may be 1:1 to 1:100.
In themetallocene catalyst according to the present disclosure, as the support, a support containing a hydroxy group on its surface can be used, and preferably a support having a highly reactive hydroxy group and siloxane group, of which the surface is dried and removed of moisture, can be used.
For example, silica, silica-alumina, silica-magnesia, or the like, which are dried at high temperature, can be used, and they may typically contain oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.
The drying temperature of the support is preferably 200 to 800 C, more preferably 300 to 600 C, and most preferably 300 to 400 C. If the drying temperature of the support is lower than 200 C, it retains excessive moisture such that moisture on the surface is reacted with the cocatalyst. If the drying temperature is higher than 800 C, pores on the surface of the support are combined with each other to reduce the surface area, and many hydroxyl groups are lost Date Recue/Date Received 2021-08-03 on the surface to leave only siloxane groups. Thus, since the reactive sites with cocatalyst are reduced, it is not preferable.
The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g.
The amount of hydroxyl groups on the surface of the support may be controlled depending on the preparation method and conditions of the support, or drying conditions such as temperature, time, vacuum, spray drying, and the like.
If the amount of hydroxyl groups is less than 0.1 mmol/g, the reactive sites with the cocatalyst are reduced. If the amount of hydroxyl groups is more than 10 mmol/g, it is not desirable because it may be caused by moisture in addition to the hydroxyl groups present on the surface of support particles.
Meanwhile, the polyethylene according to the present disclosure can be prepared by polymerizing an ethylene monomer in the presence of the above-described hybrid metallocene catalyst.
Alternatively, according to an embodiment of the present disclosure, it may be prepared by copolymerizing an ethylene monomer and another olefinic comonomer together.
Specific examples of the olefinic monomer may include 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, and the like, and these monomers may be copolymerized by mixing two or more thereof.
In the case where the olefinic polymer is an ethylene/alpha-Date Recue/Date Received 2021-08-03 olefin copolymer, the content of alpha-olefin as a comonomer is not particularly limited, and it may be appropriately selected according to the use or purpose of the olefinic polymer.
The polymerization reaction may be carried out by polymerizing monomers, using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
And, the polymerization temperature may be about 25 to about 500 C, preferably about 25 to about 200 C, and more preferably about 50 to about 150 C. Further, the polymerization pressure may be from about Ito about 100 Kgfice, preferably from about Ito about 50 Kgfice, and more preferably from about 5 to about 30 Kgfice.
The metallocene catalyst may be injected after being dissolved or diluted in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene. It is preferable that the solvent is used after a small amount of water, air, or the like acting as a catalyst poison is removed by treating with a small amount of aluminum. It can also be performed by further using a cocatalyst.
According to another embodiment of the present disclosure, a crosslinked polyethylene pipe including the polyethylene is provided.
The crosslinked polyethylene pipe of the present disclosure Date Recue/Date Received 2021-08-03 may be produced by subjecting the above-mentioned polyethylene to RAM extrusion molding. The RAM extrusion molding is used in the extrusion molding field where uniform and high pressure is required, and has the effect of processing a high molecular weight polyethylene resin during production of a crosslinked polyethylene pipe, as compared with a screw-type extrusion molding.
The RAM extrusion molding may be performed by a method used for producing a conventional crosslinked polyethylene pipe, and is not particularly limited.
Further, in the production of the crosslinked polyethylene pipe, a conventional crosslinking agent, an antioxidant and the like can be mixed together with the polyethylene of the present disclosure to perform extrusion.
As the crosslinking agent, an organic peroxide crosslinking agent may be used. Specific examples of the organic peroxide crosslinking agent may include di-t-butyl peroxide (DTBP), dicumyl peroxide, di-t-amyl peroxide, 2,5-dimethy1-2,5-di(t-butylperoxy)hexane, and the like, but the present disclosure is not limited thereto. Further, the content of the crosslinking agent is not particularly limited, but it may be contained in an amount of 0.4 to 1 part by weight based on 100 parts by weight of polyethylene.
As the antioxidant, a phenolic antioxidant may be used.
Specific examples of the phenolic antioxidant may include IRGANOX
1076, IRGANOX 1010, BHT, songnox 1076, and the like, but the present disclosure is not limited thereto. In addition, the content of Date Recue/Date Received 2021-08-03 the antioxidant is not particularly limited, but it may be contained in an amount of 0.1 to 0.6 parts by weight based on 100 parts by weight of polyethylene.
Further, the crosslinked pipe may be a PE-Xa pipe.
Further, the polyethylene according to an embodiment of the present disclosure may have a degree of crosslinking of 70% or more as measured according to KS M ISO 10147.
More specifically, according to one embodiment, the polyethylene of the present disclosure has a degree of crosslinking of 70% or more, or 75% or more, or 77% or more, or 80% or more, or 82% or more, or 83% or more, and 99% or less, or 96% or less, or 92%
or less as measured according to KS M ISO 10147.
By having the high degree of crosslinking of 70% or more as described above, the polyethylene of the present disclosure may have excellent mechanical strength.
Hereinafter, preferred embodiments are presented to aid in understanding the present disclosure. However, the following examples are provided for a better understanding of the present disclosure, and the contents of the present disclosure are not limited thereto.
<EXAMPLE>
<Synthesis Example of Metallocene Compound>
Synthesis Example 1: Synthesis of First Metallocene Compound Date Recue/Date Received 2021-08-03 ""-si =ZrCl2 c>4----0=7 ====.õ===
1-1 Preparation of Ligand Compound 2.9 g (7.4 mmol) of 8-methyl-5-(2-(trifluoromethyl)benzyI)-5,10-dihydroindeno[1,2-b]indole was dissolved in 100 mL of hexane and 2 mL(16.8 mmol) of MTBE (methyl tertiary butyl ether), and 3.2 mL (8.1 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, and then the mixture was stirred at room temperature overnight. 2 g (7.4 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane in another 250 mL Schlenk flask, and then added dropwise in a dry ice/acetone bath, and a lithiated slurry of 8-methyl-5-(2-(trifluoromethyl)benzy1)-5,10-dihydroindeno[1,2-b]indole was added dropwise via a cannula. After the injection was completed, the mixture was slowly raised to room temperature and then stirred at room temperature overnight. At the same time, 1.2 g (7.4 mmol) of fluorene was also dissolved in 100 mL of THF, and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, and the mixture was stirred at room temperature Date Recue/Date Received 2021-08-03 overnight.
Reaction solution (Si solution) of 8-methy1-5-(2-(trifluoromethyl)benzy1)-5,10-dihydroindeno[1,2-b]indole and (6-(tert-butoxy)hexyl)dichloro(methyl)silane was subjected to NMR sampling to confirm the completion of the reaction.
1H NMR (500 MHz, CDC13): 7.74-6.49 (11H, m), 5.87 (2H, s), 4.05 (1H, d), 3.32 (2H, m), 3.49 (3H, s), 1.50-1.25(8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17 (3H, d) After confirming the synthesis first, a lithiated solution of fluorene was slowly added dropwise to the Si solution in a dry ice/acetone bath, and then the mixture was stirred at room temperature overnight. After the reaction, extraction was performed with ether/water, and residual moisture in the organic layer was removed with MgSO4, and then the solvent was removed under vacuum and reduced pressure conditions to obtain 5.5 g (7.4 mmol) of the oily ligand compound, which could be confirmed by 1H-NMR.
1H NMR (500 MHz, CDC13): 7.89-6.53 (19H, m), 5.82 (2H, s), 4.26 (1H, d), 4.14-4.10 (1H, m), 3.19 (3H, s), 2.40 (3H, m), 1.35-1.21 (6H, m), 1.14 (9H, s), 0.97-0.9 (4H, m), -0.34 (3H, t).
1-2 Preparation of Metallocene Compound 5.4 g (Mw 742.00, 7.4 mmol) of the ligand compound synthesized in 1-1 was dissolved in 80 mL of toluene and 3 mL (25.2 mmol) of MTBE, and 7.1 mL (17.8 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred at room temperature overnight. 3.0 g (8.0 mmol) of ZrC14(THF)2 was Date Recue/Date Received 2021-08-03 added to 80 mL of toluene to prepare a slurry. 80 mL of ZrCI4(THF)2 as a toluene slurry was transferred to a ligand-Li solution in a dry ice/acetone bath and stirred at room temperature overnight.
The reaction mixture was filtered to remove LiCI, the filtrate was dried under vacuum to remove toluene, and then 100 mL of hexane was added thereto and sonicated for 1 hour. This was filtered to obtain 3.5 g of a purple metallocene compound as a filtered solid (yield 52 mol %).
1H NMR (500 MHz, CDCI3): 7.90-6.69 (9H, m), 5.67 (2H, s), 3.37 (2H, m), 2.56 (3H,$), 2.13-1.51 (11H, m), 1.17 (9H, s).
Synthesis Example 2. Synthesis of Second Metallocene Compound Preparation of [tBu-0-(CII2)6-05H412ZrC12 Tert-Butyl-0-(CH2)6-CI was prepared using 6-chlorohexanol by the method suggested in the literature [Tetrahedron Lett. 2951 (1988)], and reacted with NaCp to obtain t-Butyl-0-(CH2)6-C31-13 (yield:
60%, b.p. 80 C / 0.1 mmHg).
Further, t-butyl-0-(CH2)6-C31-13 was dissolved in THF at -78 C, n-butyllithium (n-BuLi) was slowly added thereto, the reaction temperature was raised to room temperature, and the mixture was then allowed to react for 8 hours. The solution was again reacted in which the already synthesized lithium salt solution was slowly added to a suspension solution of ZrCI4(THF)2 (1.70g, 4.50mm01)/THF(30ne) at -78 C and further reacted at room temperature for 6 hours.
All volatile substances were vacuum dried, and a hexane Date Recue/Date Received 2021-08-03 solvent was added to the obtained oily liquid substance and the mixture was filtered out. The filtered solution was vacuum dried, and then hexane was added thereto to induce a precipitate at low temperature (-20 C). The obtained precipitate was filtered off at a low temperature to obtain a [tBu-0-(CH2)6-05H4]2ZrCl2 compound as a white solid (yield: 92%).
1H NMR (300 MHz, CDCI3): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J
= 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 (t, J = 8 Hz), 1.7 - 1.3 (m, 8 H), 1.17 (s, 9 H).
13C NMR (CDC13): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.
<Preparation Example of Hybrid Supported Catalyst>
Preparation Example 1 5.0 kg of a toluene solution was added to a 20 L sus autoclave, and the reactor temperature was maintained at 40 C. 1000 g of silica (produced by Grace Davison, SP 948) was dehydrated by applying vacuum for 12 hours at a temperature of 600 C, and then added to a reactor to sufficiently disperse the silica. 495 g of the first metallocene compound of Synthesis Example 1 was then dissolved in toluene and then added thereto. The mixture was allowed to react while stirring at 200 rpm at 40 C for 2 hours. Then, the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted.
2.5 kg of toluene was added to the reactor, and 9.4 kg of a 10 Date Recue/Date Received 2021-08-03 wt% methylaluminoxane (MAO)/toluene solution was added thereto, and the mixture was stirred at 200 rpm at 40 C for 12 hours. After the reaction, the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted. 3.0 kg of toluene was added thereto and stirred for 10 minutes, then the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted.
3.0 kg of toluene was added to the reactor, and 28 g of the second metallocene compound of Synthesis Example 2 was dissolved in 1 L of a toluene solution and added to the reactor, and allowed to react while stirring at 200 rpm at 40 C for 2 hours. After lowering the reactor temperature to room temperature, the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted.
2.0 kg of toluene was added to the reactor and stirred for 10 minutes. Then, stirring was stopped, and the reaction solution was settled for 30 minutes, and decanted.
3.0 kg of hexane was added to the reactor, a hexane slurry was transferred to a filter dryer, and the hexane solution was filtered.
The filtrate was dried under reduced pressure at 40 C for 4 hours to prepare 1 kg of a 5i02 hybrid supported catalyst (molar ratio between the first metallocene compound and the second metallocene compound was 10:1).
Preparation Example 2 The hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, except that 476 g of the first Date Recue/Date Received 2021-08-03 metallocene compound of Synthesis Example 1 was added, and 34 g of the second metallocene compound of Synthesis Example 2 was added. In the prepared hybrid supported catalyst, the molar ratio between the first metallocene compound and the second metallocene compound was 8:1.
<Polyethylene Polymerization>
Example 1 The supported catalyst prepared in Preparation Example 1 was added to a single slurry polymerization process to prepare a high-density polyethylene.
First, hexane was injected at a flow rate of 25 ton/hr, ethylene at 10 ton/hr, hydrogen at 20 ppm (relative to ethylene), and triethyl aluminum (TEAL) at 10 kg/hr into a reactor with a capacity of 100 m3, respectively. Further, the hybrid supported metallocene catalyst according to Preparation Example 1 was injected at 0.5 kg/hr. Then, ethylene was continuously reacted in the form of a hexane slurry at a reactor temperature of 82 C and a pressure of 7.0 kg/cm2 to 7.5 kg/cm2, and then subjected to solvent removal and drying process to prepare high density polyethylene in powder form.
Example 2 The high-density polyethylene in powder form was prepared in the same manner as in Example 1, except that the amount of hydrogen charged was 30 ppm relative to ethylene.
Example 3 The high-density polyethylene in powder form was prepared in Date Recue/Date Received 2021-08-03 the same manner as in Example 1, except that the supported catalyst prepared in Preparation Example 2 was charged into a single slurry polymerization process.
Comparative Example 1 The polyethylene prepared using a Ziegler-Natta catalyst, XL1800 product by LG Chem, was used as Comparative Example 1.
Comparative Example 2 The polyethylene prepared using a Ziegler-Natta catalyst, 8100GX product by Lotte Chemical, was used as Comparative Example 2.
<Production of Crosslinked Polyethylene Pipe>
Example 4 100 g of polyethylene of Example 1 was mixed with 0.3 g of n-octadecy1-3-(3,5-di-tert.buty1-4-hydroxypheny1)-propionate (product name lrganox 1076, produced by BASF) as an antioxidant and 0.6 g of di-tert-butyl peroxide (product name: Trigonox B, produced by Akzo Nobel) as a crosslinking agent, and dispersed using a Henschel! Mixer (RPM 400, mixing time 15min, mix temp <40 C).
Subsequently, in order to produce the crosslinked polyethylene pipe, extrusion was performed with a Ram type extruder.
At this time, the pipe diameter of the extruder was set to 20mm, the thickness was set to 1.9mm, and the linear velocity during pipe extrusion was set to 2.2m/min. Temperature conditions were set to Body 130 C, Adaptor 180 C, Die - 240 C.
Date Recue/Date Received 2021-08-03 Example 5 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Example 2 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 2.1 m/min.
Example 6 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Example 3 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 2.1 m/min.
Comparative Example 3 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Comparative Example 1 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 1.8 m/min.
Comparative Example 4 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Comparative Example 2 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 1.8 m/min.
Comparative Example 5 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Date Recue/Date Received 2021-08-03 Comparative Example 1 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 2.2 m/min.
<Experimental Example>
Evaluation of Physical Properties Physical properties of the polyethylene and the crosslinked polyethylene pipes produced in the Examples and Comparative Examples were evaluated by the following method.
(1) Weight average molecular weight (Mw) and molecular weight distribution (MWD, polydispersity index), GPC curve:
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured using a gel permeation chromatography (GPC; produced by Waters Corp.), and the polydispersity index (PDI) was calculated by dividing the weight average molecular weight into the number average molecular weight.
Specifically, polyethylene sample was evaluated using a Waters PL-GPC220 instrument using a PLgel Mixed-B column (300 mm in length) from Polymer Laboratories, wherein an evaluation temperature was set to 160 C, 1,2,4-trichlorobenzene was used as a solvent, and a flow rate was set to 1 mL/min. In addition, a sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 pL. A calibration curve formed by using a polystyrene standard was used to determine Mw and Mn values. The Date Recue/Date Received 2021-08-03 molecular weight of the polystyrene standard used was nine types of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 /
4,000,000 / 10,000,000.
(2) Melt Index (M121.6):
Measured according to the ASTM D1238 standard (Condition E, 190 C, 21.6 kg load).
(3) Density: Measured according to the ASTM D792 standard.
(4) Log Mw (6.0): Through the GPO curve graph measured in the above (1), it was calculated by the ratio of the integration value in a region where the Log Mw value is 6.0 or more relative to the entire area (integration value) of the entire GPC curve graph.
(5) crosslinking rate (T90, min) The crosslinking rate was measured according to ASTM D
5289, and was evaluated by measuring the time T90 until it became 90% of the maximum torque when a vulcanization curve was measured at 180 C for 30 minutes by a vulcanization tester (equipment name: Premier MDR, produced by Alpha Technologies).
The vibrational motion at this time was performed at 1Hz.
It means that as the value of T90 is smaller, the crosslinking proceeds faster, and that as the value is large, the crosslinking proceeds more slowly.
At this time, the sample used in the experiment was prepared as follows. First, 100 g of polyethylene, 0.3 g of antioxidant (Irganox 1076), and 0.6 g of crosslinking agent (di-tert-butyl peroxide) were mixed, and then the soaking time was set to 6 hours or more. Then, Date Recue/Date Received 2021-08-03 the press device (device name: Presses Type E, produced by Collin) was used to perform a melt process at 140 C and 30 bar for 4 minutes, and then prepared into a 2T sheet for use.
(6) Linear velocity During pipe production, the length produced for 1 minute with the portion passing through the water bath was measured three times using a tape measure, and the average value was taken as the linear velocity (unit: m/min).
(6) Degree of crosslinking: Measured according to KS M ISO
10147.
[Table 1]
Crosslinked Example Example Example Comparative Comparative Comparative polyethylene 4 5 6 Example 3 Example 4 Example 5 Polyethylene Example Example Example Comparative Comparative Comparative 1 2 3 Example 1 Example 2 Example 1 Mn (g/mol) 45,000 36,000 49,000 53,900 52,000 53,900 Mw (g/mol) 284,000 248,000 219,000 221,000 231,000 221,000 MWD 6.2 6.8 4.6 3.9 4.1 3.9 M 121 6 2.0 4.0 2.9 2.0 1.5 2.0 (g/10mi) Density 0.948 0.948 0.948 0.948 0.945 0.948 (g/cm3) Date Recue/Date Received 2021-08-03 Log MW 7.6 6.2 4/ 3.2 3.5 3.2 6.0 (%)*
T90 (min) 8.9 9.4 9.9 10.2 10.5 10.2 Linear 2.2 2.1 2.1 1.8 1.8 2.2 velocity (m/min) Degree of 86 86 83 87 75 80 crosslinking (%) * the ratio of the integration value of the area where the log Mw value was 6.0 or more relative to the total integral value, in the GPC curve graph where the x-axis is log Mw and the y-axis is dw/dlogMw.
Referring to Table 1, the polyethylene of Examples 1 to 3 according to the present disclosure exhibited a high content of ultra-high molecular weight, with the ratio of the integration value of the area where the log Mw value was 6.0 or more to the total integral value being 4.5% or more in the GPC curve graph.
Therefore, despite the crosslinking reaction proceeds rapidly with the crosslinking rate (T90) of less than 10 minutes during crosslinking, and even though extrusion was performed at a high linear velocity of 2.0m/min or more, the degree of crosslinking was shown to be equal to or superior to that of Comparative Examples.
Date Recue/Date Received 2021-08-03
Further, in the above, Mw means a weight-average molecular weight.
More specifically, according to an embodiment, the polyethylene of the present disclosure may have the integration value in a region where the Log Mw value is 6.0 or more, of 4.5% or more, or 4.7% or more, or 5% or more, or 5.2% or more, or 5.5% or more, or 6.0% or more, and 10% or less, or 9% or less, or 8.5% or less, or 8.0% or less, or 7.7% or less of the total integration value.
As described above, the integral value of the region where the Log Mw value is 6.0 or more being 4.5% or more means that the polyethylene of the present disclosure has a high molecular weight content. This improves the crosslinking rate, which is proportional to the content of the polymer in the polyethylene resin, the polyethylene of the present disclosure can achieve a higher degree of crosslinking within the same time during a crosslinking reaction with a crosslinking agent.
Therefore, when the crosslinked polyethylene is prepared using the polyethylene of the present disclosure, even when comparing with polyethylene having the same level of melt index, Date Recue/Date Received 2021-08-03 and increasing the linear velocity of the extruder than that of a conventional method, the degree of crosslinking is maintained at 70%
or more, thereby achieving an effect of improving productivity without deteriorating physical properties.
Further, when the crosslinked polyethylene is prepared using the polyethylene of the present disclosure, the crosslinking rate (T90) measured according to ASTM D 5289 shows a fast crosslinking rate of 10 minutes or less. More specifically, the crosslinking rate (T90) may be 10 minutes or less, or 9.8 minutes or less, or 9.5 minutes or less, or 9.0 minutes or less, and 5 minutes or more, or 6 minutes or more, or 7 minutes or more.
On the other hand, polyethylene according to an embodiment of the present disclosure having the physical properties as described can be prepared by a preparation method comprising polymerizing an ethylene monomer in the presence of a specific metallocene compound as a catalytically active component.
More specifically, the polyethylene of the present disclosure includes, but not limited thereto, a first metallocene compound represented by the following Chemical Formula 1; and a second metallocene compound represented by the following Chemical Formula 3, and can be prepared by polymerizing an ethylene monomer in the presence of a hybrid metallocene catalyst in which a molar ratio between the first metallocene compound and the second metallocene compound is 20:1 to 5:1.
[Chemical Formula 1]
Date Recue/Date Received 2021-08-03 Cl Qi \\*
/*/MI
in the Chemical Formula 1, Qi and Q2 are the same as or different from each other, and each independently represents hydrogen, a halogen, a Cl to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
B is carbon, silicon, or germanium;
Mi is a Group 4 transition metal;
Xi and X2 are the same as or different from each other, and each independently represents a halogen, a Cl to C20 alkyl group, a C2 to C10 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
one of Ci and C2 is represented by the following Chemical Formula 2a or Chemical Formula 2b, and the other of Ci and C2 is represented by the following Chemical Formula 2c;
[Chemical Formula 2a]
Date Recue/Date Received 2021-08-03 [Chemical Formula 2b]
R2' Rs' R8' R8' R5' Ric; RI21 R11' [Chemical Formula 2c]
R20 O.* R15 in the Chemical Formulas 2a, 2b and 2c, Ri to R21 and Ri' to R13' are the same as or different from each other, and each independently represents hydrogen, a halogen, Date Recue/Date Received 2021-08-03 a Cl to C20 alkyl group, a Cl to C20 haloalkyl group, a C2 to C20 alkenyl group, a Cl to C20 alkylsilyl group, a Cl to C20 silylalkyl group, a Cl to C20 alkoxysilyl group, a Cl to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, provided that at least one of R9 to R13 and R9' to R13' is a Cl to C20 haloalkyl group, [Chemical Formula 3]
Cpe'r- 'X4 in the Chemical Formula 3, M2 is a Group 4 transition metal;
Cpi and Cp2 are the same as or different from each other, and each independently represents any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-l-indenyl and fluorenyl, one or more hydrogens of the cyclic group may be each independently substituted with any one substituent selected among a Cl to 20 alkyl, a Cl to C20 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl; and X3 and X4 are the same as or different from each other, and each independently represents a halogen, a Cl to C20 alkyl, a C2 to C10 alkenyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl.
The substituents of Chemical Formulas 1 and 2 will be described in more detail below.
Date Recue/Date Received 2021-08-03 The Cl to C20 alkyl group includes a linear or branched alkyl group, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like may be mentioned, but is not limited thereto.
The C2 to C20 alkenyl group includes a linear or branched alkenyl group, and specifically, an allyl group, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and the like may be mentioned, but is not limited thereto.
The C6 to C20 aryl group includes a monocyclic or condensed ring aryl group, and specifically, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, and the like may be mentioned, but is not limited thereto.
The Cl to C20 alkoxy group may include, but not limited to, a methoxy group, an ethoxy group, a phenyloxy group, and a cyclohexyloxy group.
The C2 to C20 alkoxyalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with an alkoxy group, and specifically, alkoxyalkyl groups such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhexyl group, a tert-butoxymethyl group, a tert-butoxyethyl group and a tert-butoxyhexyl group; or aryloxyalkyl groups such as a phenoxyhexyl group may be mentioned, but is not limited thereto.
Date Recue/Date Received 2021-08-03 The Cl to C20 alkylsilyl group or the Cl to C20 alkoxysilyl group is a functional group in which 1 to 3 hydrogens of -SiH3 are substituted with 1 to 3 alkyl or alkoxy groups as described above, and specifically, alkylsilyl groups such as a methylsilyl group, a dimethylsilyl group, a trimethylsilyl group, a dimethylethylsilyl group, a diethylmethylsilyl group, or a dimethylpropylsilyl group; alkoxysilyl groups such as a methoxysilyl group, a dimethoxysilyl group, a trimethoxysilyl group or a dimethoxyethoxysilyl group; alkoxyalkylsilyl groups such as a methoxydimethylsilyl group, a diethoxymethylsilyl group, or a dimethoxypropylsilyl group may be mentioned, but is not limited thereto.
The Cl to C20 silylalkyl group is a functional group in which at least one hydrogen of the alkyl group as described above is substituted with a silyl group, and specifically, -CH2-SiH3, a methylsilylmethyl group, or a dimethylethoxysilylpropyl group may be mentioned, but are not limited thereto.
The halogen may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).
The above-described substituents may be optionally substituted with one or more substituents selected from the group consisting of a hydroxy group; a halogen; an alkyl group or an alkenyl group, an aryl group, an alkoxy group; an alkyl or an alkenyl group, an aryl group, or an alkoxy group including at least one heteroatom selected among the heteroatoms of Groups 14 to 16; a silyl group; an alkylsilyl group or an alkoxysilyl group; a phosphine Date Recue/Date Received 2021-08-03 group; a phosphide group; a sulfonate group; and a sulfone group which are within a range exhibiting the same or similar effect as the desired effect.
The Group 4 transition metal may include titanium (Ti), zirconium (Zr), and hafnium (Hf), but are not limited thereto.
According to an embodiment of the present disclosure, Ri to R21 and Ri' to R13' in Chemical Formulas 2a, 2b, and 2c may be each independently hydrogen, a halogen, a Cl to C20 alkyl group, or a Cl to C20 haloalkyl group, and at least one of R9 to R13 and R9' to R13' may be a Cl to C20 haloalkyl group.
More specifically, Ri to R21 and Ri' to Ri3' may be each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, or a fluoroalkyl group, and at least one of R9 to R13 and R9' to Ri3' may be fluoroalkyl, but is not limited thereto.
According to an embodiment of the present disclosure Qi and Q2 in Chemical Formula 1 may be each independently hydrogen, a halogen, a Cl to C20 alkyl group, or a C2 to C20 alkoxyalkyl group.
More specifically, Qi and Q2 may be each independently hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a methoxymethyl group, a tert-butoxymethyl group, a tert-butoxyhexyl group, 1-ethoxyethyl group, 1-methyl-l-methoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group, but are not Date Recue/Date Received 2021-08-03 limited thereto.
According to an embodiment of the present disclosure, B in Chemical Formula 1 is preferably silicon, but is not limited thereto.
According to an embodiment of the present disclosure, Xi and X2 in Chemical Formula 1 may be each independently a halogen or a C1 to C20 alkyl group.
The first metallocene compound of Chemical Formula 1 forms a structure in which an indeno-indole derivative and a cyclopentadiene derivative are asymmetrically crosslinked by a bridge, and by having a non-shared electron pair capable of functioning as a Lewis base in the ligand structure, it is supported on the surface having Lewis acid properties of the support, and exhibits high polymerization activity even when supported. Further, by including the electronically rich indeno-indole group and cyclopentadiene group, the activity is high, and excellent copolymerization property and high activity are maintained due to appropriate steric hindrance and the electronic effect of the ligand.
Moreover, beta-hydrogen of the polymer chain in which the nitrogen atom of the indeno-indole derivative grows can be stabilized by hydrogen bonding to suppress beta-hydrogen elimination and polymerize an ultra-high molecular weight polyolefin.
In particular, one or more of R9 to Ri3 and R9' to R13' in the transition metal compound of Chemical Formula 1 includes a C1-C20 haloalkyl group. Further, haloalkyl groups containing halogen elements other than other fluorine may also interact with beta-Date Recue/Date Received 2021-08-03 hydrogen, but hydrogen forms a hydrogen bond with highly electronegative atoms such as nitrogen, oxygen, and fluorine. All haloalkyl groups do not form a hydrogen bond with beta-H. It does not form a hydrogen bond with beta-H by including a haloalkyl group, but is an effect exhibited by introducing a fluorine substituent. For example, a fluoroalkyl group, that is, CF3, etc. may be mentioned. It acts like the nitrogen atom of the indeno-indole derivative, stabilizes beta-hydrogen of a growing polymer chain by hydrogen bonding, further suppresses beta-hydrogen elimination, and more effectively can achieve the polymerization of the ultra-high molecular weight polyolefin. In other words, it maintains the basic skeleton of the catalyst in which the indeno-indole derivative and the cyclopentadiene derivative are asymmetrically crosslinked by a bridge, and by introducing substituents such as CF3 which is a stronger hydrogen bond acceptor, beta-hydrogen is stabilized by hydrogen bonding, thereby enhancing the effect of suppressing beta-hydrogen elimination and enabling the polymerization of ultra-high molecular weight polyolefin.
According to an embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 2a may include a compound represented by the following structural formula, but the present disclosure is not limited thereto.
Date Recue/Date Received 2021-08-03 0 r.
0.
According to an embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 2b may be a compound represented by the following structural formula, but the present disclosure is not limited thereto.
According to an embodiment of the present disclosure, specific examples of the compound represented by Chemical Formula 2c may include a compound represented by one of the following structural formulas, but the present disclosure is not limited thereto.
=
Date Recue/Date Received 2021-08-03 Oa* d<
--,--' According to an embodiment of the present disclosure, specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by Chemical Formula 1-1, but the present disclosure is not limited thereto.
[Structural Formula 1-1]
F3o ,.:-._:-----\
N
Si' ZrCl2 >
,/ 0(-1 ...
'-'7\/0 The first metallocene compound may be synthesized by applying known reactions, and for a more detailed synthesis method, please refer to Examples.
According to an embodiment of the present disclosure, Cpi and Cp2 in Chemical Formula 3 may be each independently cyclopentadienyl or indenyl, and at least one hydrogen of the cyclopentadienyl or indenyl may be each independently substituted Date Recue/Date Received 2021-08-03 with any one substituent selected among a Cl to 20 alkyl or a C2 to C20 alkoxyalkyl.
According to an embodiment of the present disclosure, M2 in Chemical Formula 3 is preferably zirconium (Zr), but the present disclosure is not limited thereto.
According to an embodiment of the present disclosure, X3 and X4 in Chemical Formula 3 may be each independently a halogen or a Cl to C20 alkyl group.
The second metallocene compound represented by Chemical Formula 3 may be, for example, a compound represented by one of the following structural formulas, but the present disclosure is not limited thereto.
)1/4sCt-412 .aca2 ro Zrd2 \rCl2 >Lo LO
C)Ctieli rCl2 Date Recue/Date Received 2021-08-03 ' 4.40-1,3L_C ZrC' jZiC 12 ZoCl2 Ci" ( = 4041I
'ZrC12 Further, the second metallocene compound represented by Chemical Formula 3 may be more preferably represented by the following Formula 3-1:
[Chemical Formula 3-1]
>r ZrC42 )%0PSØ-Nir's\AsS
The second metallocene compound represented by Chemical Formula 3 may be synthesized by applying known reactions, and for a more detailed synthesis method, refer to Examples.
In the hybrid metallocene catalyst according to an embodiment of the present disclosure, the first metallocene compound represented by Chemical Formula 1 can mainly contribute to the Date Recue/Date Received 2021-08-03 expression of high molecular weight polyethylene, and the second metallocene compound represented by Chemical Formula 3 can mainly contribute to the expression of low molecular weight polyethylene with a narrow molecular weight distribution.
As the hybrid metallocene catalyst according to an embodiment of the present disclosure uses as a hybrid metallocene catalyst using a metallocene compound with a low molecular weight expression having a narrow polydispersity index and a metallocene compound with a high molecular weight expression together, it is advantageous for polymerizing the polyethylene of the present disclosure described above.
In the hybrid metallocene catalyst of the present disclosure, the molar ratio between the first metallocene compound represented by Chemical Formula 1 and the second metallocene compound represented by Chemical Formula 3 may be 20:1 to 5:1, or 18:1 to 7:1, or 15:1 to 8:1. At this time, when the molar ratio of the first and second metallocene compounds exceeds 20:1 and the content of the first metallocene compound is too large, the density is reduced and the pipe pressure resistance can be deteriorated. When the molar ratio is less than 5: 1 and the content of the first metallocene compound is too small, the crosslinking rate can become slow.
Therefore, from such a viewpoint, the molar ratio of the first and second metallocene compounds may be preferably in the above-described range.
In the hybrid metallocene catalyst used in the present Date Recue/Date Received 2021-08-03 disclosure, one or more of the first metallocene compound represented by Chemical Formula 1 and one or more of the second metallocene compound represented by Chemical Formula 3 may be supported on respective supports together with a cocatalyst compound.
In the hybrid metallocene catalyst of the present disclosure, the cocatalyst supported together on the support for activating the first and second metallocene compounds is an organometallic compound containing a Group 13 metal, and it is not particularly limited as long as it can be used when polymerizing olefins under a general metallocene catalyst.
Specifically, the cocatalyst compound may include at least one selected among an aluminum-containing first cocatalyst of the following Chemical Formula 4 and a borate-based second cocatalyst of the following Chemical Formula 5.
[Chemical Formula 4]
-[Al(Ra)-0]k-in the Chemical Formula 4, each Ra is independently a halogen, a halogen-substituted or unsubstituted hydrocarbyl group having 1 to 20 carbon atoms, and k is an integer of 2 or more, [Chemical Formula 5]
T[BG4]-in the Chemical Formula 5, T+ is a +1 charge polyatomic ion, B
is boron in an oxidation state of +3, each G is independently selected from the group consisting of a hydride group, a dialkylamido group, a Date Recue/Date Received 2021-08-03 halide group, an alkoxide group, an aryloxide group, a hydrocarbyl group, a halocarbyl group, and a halo-substituted hydrocarbyl group, wherein the G has 20 or less carbon atoms, provided that G is a halide at one or less position.
By using the first and second cocatalysts as described above, the polymerization activity can be further enhanced.
The first cocatalyst of Chemical Formula 4 may be an alkylaluminoxane-based compound wherein the repeating units are combined into a linear, circular, or network form. Specific examples of the first cocatalyst include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.
Further, the second cocatalyst of Chemical Formula 5 may be a trisubstituted ammonium salt, a dialkylammonium salt, or a trisubstituted phosphate type of borate compound. Specific examples of the second cocatalyst include a borate-based compound in the form of a trisubstituted ammonium salt, such as trimethylammonium tetraphenylborate, methyl dioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyloctadecylammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilinium)tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, methylditetradecylammonium Date Recue/Date Received 2021-08-03 tetrakis(pentaphenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N, N-dimethylanilin ium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N, N-dimethyl(2,4,6-trimethylanilinium )tetrakis(pentafluorophenyl)borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate or N,N-dimethyl-(2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl)borate and the like; a borate-based compound in the form of a dialkylammonium salt, such as dioctadecylammonium tetrakis(pentafluorophenyl)borate, ditetradecylammonium tetrakis(pentafluorophenyl) borate or dicyclohexylammonium tetrakis(pentafluorophenyl)borate; or a borate-based compound in the form of a trisubstituted phosphonium salt, such as triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, or Date Recue/Date Received 2021-08-03 tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate.
In the metallocene catalyst according to the present disclosure, the mass ratio of the total weight of the transition metals contained in the first and second metallocene compounds relative to the support may be 1 : 10 to 1 : 1,000. When the support and the metallocene compound are contained in the range of the above mass ratio, an optimal shape can be provided. Further, the mass ratio of the cocatalyst compound to the support may be 1:1 to 1:100.
In themetallocene catalyst according to the present disclosure, as the support, a support containing a hydroxy group on its surface can be used, and preferably a support having a highly reactive hydroxy group and siloxane group, of which the surface is dried and removed of moisture, can be used.
For example, silica, silica-alumina, silica-magnesia, or the like, which are dried at high temperature, can be used, and they may typically contain oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.
The drying temperature of the support is preferably 200 to 800 C, more preferably 300 to 600 C, and most preferably 300 to 400 C. If the drying temperature of the support is lower than 200 C, it retains excessive moisture such that moisture on the surface is reacted with the cocatalyst. If the drying temperature is higher than 800 C, pores on the surface of the support are combined with each other to reduce the surface area, and many hydroxyl groups are lost Date Recue/Date Received 2021-08-03 on the surface to leave only siloxane groups. Thus, since the reactive sites with cocatalyst are reduced, it is not preferable.
The amount of hydroxyl groups on the surface of the support is preferably 0.1 to 10 mmol/g, and more preferably 0.5 to 5 mmol/g.
The amount of hydroxyl groups on the surface of the support may be controlled depending on the preparation method and conditions of the support, or drying conditions such as temperature, time, vacuum, spray drying, and the like.
If the amount of hydroxyl groups is less than 0.1 mmol/g, the reactive sites with the cocatalyst are reduced. If the amount of hydroxyl groups is more than 10 mmol/g, it is not desirable because it may be caused by moisture in addition to the hydroxyl groups present on the surface of support particles.
Meanwhile, the polyethylene according to the present disclosure can be prepared by polymerizing an ethylene monomer in the presence of the above-described hybrid metallocene catalyst.
Alternatively, according to an embodiment of the present disclosure, it may be prepared by copolymerizing an ethylene monomer and another olefinic comonomer together.
Specific examples of the olefinic monomer may include 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, and the like, and these monomers may be copolymerized by mixing two or more thereof.
In the case where the olefinic polymer is an ethylene/alpha-Date Recue/Date Received 2021-08-03 olefin copolymer, the content of alpha-olefin as a comonomer is not particularly limited, and it may be appropriately selected according to the use or purpose of the olefinic polymer.
The polymerization reaction may be carried out by polymerizing monomers, using a continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.
And, the polymerization temperature may be about 25 to about 500 C, preferably about 25 to about 200 C, and more preferably about 50 to about 150 C. Further, the polymerization pressure may be from about Ito about 100 Kgfice, preferably from about Ito about 50 Kgfice, and more preferably from about 5 to about 30 Kgfice.
The metallocene catalyst may be injected after being dissolved or diluted in an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof, an aromatic hydrocarbon solvent such as toluene and benzene, or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene. It is preferable that the solvent is used after a small amount of water, air, or the like acting as a catalyst poison is removed by treating with a small amount of aluminum. It can also be performed by further using a cocatalyst.
According to another embodiment of the present disclosure, a crosslinked polyethylene pipe including the polyethylene is provided.
The crosslinked polyethylene pipe of the present disclosure Date Recue/Date Received 2021-08-03 may be produced by subjecting the above-mentioned polyethylene to RAM extrusion molding. The RAM extrusion molding is used in the extrusion molding field where uniform and high pressure is required, and has the effect of processing a high molecular weight polyethylene resin during production of a crosslinked polyethylene pipe, as compared with a screw-type extrusion molding.
The RAM extrusion molding may be performed by a method used for producing a conventional crosslinked polyethylene pipe, and is not particularly limited.
Further, in the production of the crosslinked polyethylene pipe, a conventional crosslinking agent, an antioxidant and the like can be mixed together with the polyethylene of the present disclosure to perform extrusion.
As the crosslinking agent, an organic peroxide crosslinking agent may be used. Specific examples of the organic peroxide crosslinking agent may include di-t-butyl peroxide (DTBP), dicumyl peroxide, di-t-amyl peroxide, 2,5-dimethy1-2,5-di(t-butylperoxy)hexane, and the like, but the present disclosure is not limited thereto. Further, the content of the crosslinking agent is not particularly limited, but it may be contained in an amount of 0.4 to 1 part by weight based on 100 parts by weight of polyethylene.
As the antioxidant, a phenolic antioxidant may be used.
Specific examples of the phenolic antioxidant may include IRGANOX
1076, IRGANOX 1010, BHT, songnox 1076, and the like, but the present disclosure is not limited thereto. In addition, the content of Date Recue/Date Received 2021-08-03 the antioxidant is not particularly limited, but it may be contained in an amount of 0.1 to 0.6 parts by weight based on 100 parts by weight of polyethylene.
Further, the crosslinked pipe may be a PE-Xa pipe.
Further, the polyethylene according to an embodiment of the present disclosure may have a degree of crosslinking of 70% or more as measured according to KS M ISO 10147.
More specifically, according to one embodiment, the polyethylene of the present disclosure has a degree of crosslinking of 70% or more, or 75% or more, or 77% or more, or 80% or more, or 82% or more, or 83% or more, and 99% or less, or 96% or less, or 92%
or less as measured according to KS M ISO 10147.
By having the high degree of crosslinking of 70% or more as described above, the polyethylene of the present disclosure may have excellent mechanical strength.
Hereinafter, preferred embodiments are presented to aid in understanding the present disclosure. However, the following examples are provided for a better understanding of the present disclosure, and the contents of the present disclosure are not limited thereto.
<EXAMPLE>
<Synthesis Example of Metallocene Compound>
Synthesis Example 1: Synthesis of First Metallocene Compound Date Recue/Date Received 2021-08-03 ""-si =ZrCl2 c>4----0=7 ====.õ===
1-1 Preparation of Ligand Compound 2.9 g (7.4 mmol) of 8-methyl-5-(2-(trifluoromethyl)benzyI)-5,10-dihydroindeno[1,2-b]indole was dissolved in 100 mL of hexane and 2 mL(16.8 mmol) of MTBE (methyl tertiary butyl ether), and 3.2 mL (8.1 mmol) of a 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, and then the mixture was stirred at room temperature overnight. 2 g (7.4 mmol) of (6-tert-butoxyhexyl)dichloro(methyl)silane was dissolved in 50 mL of hexane in another 250 mL Schlenk flask, and then added dropwise in a dry ice/acetone bath, and a lithiated slurry of 8-methyl-5-(2-(trifluoromethyl)benzy1)-5,10-dihydroindeno[1,2-b]indole was added dropwise via a cannula. After the injection was completed, the mixture was slowly raised to room temperature and then stirred at room temperature overnight. At the same time, 1.2 g (7.4 mmol) of fluorene was also dissolved in 100 mL of THF, and 3.2 mL (8.1 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath, and the mixture was stirred at room temperature Date Recue/Date Received 2021-08-03 overnight.
Reaction solution (Si solution) of 8-methy1-5-(2-(trifluoromethyl)benzy1)-5,10-dihydroindeno[1,2-b]indole and (6-(tert-butoxy)hexyl)dichloro(methyl)silane was subjected to NMR sampling to confirm the completion of the reaction.
1H NMR (500 MHz, CDC13): 7.74-6.49 (11H, m), 5.87 (2H, s), 4.05 (1H, d), 3.32 (2H, m), 3.49 (3H, s), 1.50-1.25(8H, m), 1.15 (9H, s), 0.50 (2H, m), 0.17 (3H, d) After confirming the synthesis first, a lithiated solution of fluorene was slowly added dropwise to the Si solution in a dry ice/acetone bath, and then the mixture was stirred at room temperature overnight. After the reaction, extraction was performed with ether/water, and residual moisture in the organic layer was removed with MgSO4, and then the solvent was removed under vacuum and reduced pressure conditions to obtain 5.5 g (7.4 mmol) of the oily ligand compound, which could be confirmed by 1H-NMR.
1H NMR (500 MHz, CDC13): 7.89-6.53 (19H, m), 5.82 (2H, s), 4.26 (1H, d), 4.14-4.10 (1H, m), 3.19 (3H, s), 2.40 (3H, m), 1.35-1.21 (6H, m), 1.14 (9H, s), 0.97-0.9 (4H, m), -0.34 (3H, t).
1-2 Preparation of Metallocene Compound 5.4 g (Mw 742.00, 7.4 mmol) of the ligand compound synthesized in 1-1 was dissolved in 80 mL of toluene and 3 mL (25.2 mmol) of MTBE, and 7.1 mL (17.8 mmol) of 2.5 M n-BuLi hexane solution was added dropwise in a dry ice/acetone bath and stirred at room temperature overnight. 3.0 g (8.0 mmol) of ZrC14(THF)2 was Date Recue/Date Received 2021-08-03 added to 80 mL of toluene to prepare a slurry. 80 mL of ZrCI4(THF)2 as a toluene slurry was transferred to a ligand-Li solution in a dry ice/acetone bath and stirred at room temperature overnight.
The reaction mixture was filtered to remove LiCI, the filtrate was dried under vacuum to remove toluene, and then 100 mL of hexane was added thereto and sonicated for 1 hour. This was filtered to obtain 3.5 g of a purple metallocene compound as a filtered solid (yield 52 mol %).
1H NMR (500 MHz, CDCI3): 7.90-6.69 (9H, m), 5.67 (2H, s), 3.37 (2H, m), 2.56 (3H,$), 2.13-1.51 (11H, m), 1.17 (9H, s).
Synthesis Example 2. Synthesis of Second Metallocene Compound Preparation of [tBu-0-(CII2)6-05H412ZrC12 Tert-Butyl-0-(CH2)6-CI was prepared using 6-chlorohexanol by the method suggested in the literature [Tetrahedron Lett. 2951 (1988)], and reacted with NaCp to obtain t-Butyl-0-(CH2)6-C31-13 (yield:
60%, b.p. 80 C / 0.1 mmHg).
Further, t-butyl-0-(CH2)6-C31-13 was dissolved in THF at -78 C, n-butyllithium (n-BuLi) was slowly added thereto, the reaction temperature was raised to room temperature, and the mixture was then allowed to react for 8 hours. The solution was again reacted in which the already synthesized lithium salt solution was slowly added to a suspension solution of ZrCI4(THF)2 (1.70g, 4.50mm01)/THF(30ne) at -78 C and further reacted at room temperature for 6 hours.
All volatile substances were vacuum dried, and a hexane Date Recue/Date Received 2021-08-03 solvent was added to the obtained oily liquid substance and the mixture was filtered out. The filtered solution was vacuum dried, and then hexane was added thereto to induce a precipitate at low temperature (-20 C). The obtained precipitate was filtered off at a low temperature to obtain a [tBu-0-(CH2)6-05H4]2ZrCl2 compound as a white solid (yield: 92%).
1H NMR (300 MHz, CDCI3): 6.28 (t, J = 2.6 Hz, 2 H), 6.19 (t, J
= 2.6 Hz, 2 H), 3.31 (t, 6.6 Hz, 2 H), 2.62 (t, J = 8 Hz), 1.7 - 1.3 (m, 8 H), 1.17 (s, 9 H).
13C NMR (CDC13): 135.09, 116.66, 112.28, 72.42, 61.52, 30.66, 30.61, 30.14, 29.18, 27.58, 26.00.
<Preparation Example of Hybrid Supported Catalyst>
Preparation Example 1 5.0 kg of a toluene solution was added to a 20 L sus autoclave, and the reactor temperature was maintained at 40 C. 1000 g of silica (produced by Grace Davison, SP 948) was dehydrated by applying vacuum for 12 hours at a temperature of 600 C, and then added to a reactor to sufficiently disperse the silica. 495 g of the first metallocene compound of Synthesis Example 1 was then dissolved in toluene and then added thereto. The mixture was allowed to react while stirring at 200 rpm at 40 C for 2 hours. Then, the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted.
2.5 kg of toluene was added to the reactor, and 9.4 kg of a 10 Date Recue/Date Received 2021-08-03 wt% methylaluminoxane (MAO)/toluene solution was added thereto, and the mixture was stirred at 200 rpm at 40 C for 12 hours. After the reaction, the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted. 3.0 kg of toluene was added thereto and stirred for 10 minutes, then the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted.
3.0 kg of toluene was added to the reactor, and 28 g of the second metallocene compound of Synthesis Example 2 was dissolved in 1 L of a toluene solution and added to the reactor, and allowed to react while stirring at 200 rpm at 40 C for 2 hours. After lowering the reactor temperature to room temperature, the stirring was stopped, and the reaction solution was settled for 30 minutes and decanted.
2.0 kg of toluene was added to the reactor and stirred for 10 minutes. Then, stirring was stopped, and the reaction solution was settled for 30 minutes, and decanted.
3.0 kg of hexane was added to the reactor, a hexane slurry was transferred to a filter dryer, and the hexane solution was filtered.
The filtrate was dried under reduced pressure at 40 C for 4 hours to prepare 1 kg of a 5i02 hybrid supported catalyst (molar ratio between the first metallocene compound and the second metallocene compound was 10:1).
Preparation Example 2 The hybrid supported catalyst was prepared in the same manner as in Preparation Example 1, except that 476 g of the first Date Recue/Date Received 2021-08-03 metallocene compound of Synthesis Example 1 was added, and 34 g of the second metallocene compound of Synthesis Example 2 was added. In the prepared hybrid supported catalyst, the molar ratio between the first metallocene compound and the second metallocene compound was 8:1.
<Polyethylene Polymerization>
Example 1 The supported catalyst prepared in Preparation Example 1 was added to a single slurry polymerization process to prepare a high-density polyethylene.
First, hexane was injected at a flow rate of 25 ton/hr, ethylene at 10 ton/hr, hydrogen at 20 ppm (relative to ethylene), and triethyl aluminum (TEAL) at 10 kg/hr into a reactor with a capacity of 100 m3, respectively. Further, the hybrid supported metallocene catalyst according to Preparation Example 1 was injected at 0.5 kg/hr. Then, ethylene was continuously reacted in the form of a hexane slurry at a reactor temperature of 82 C and a pressure of 7.0 kg/cm2 to 7.5 kg/cm2, and then subjected to solvent removal and drying process to prepare high density polyethylene in powder form.
Example 2 The high-density polyethylene in powder form was prepared in the same manner as in Example 1, except that the amount of hydrogen charged was 30 ppm relative to ethylene.
Example 3 The high-density polyethylene in powder form was prepared in Date Recue/Date Received 2021-08-03 the same manner as in Example 1, except that the supported catalyst prepared in Preparation Example 2 was charged into a single slurry polymerization process.
Comparative Example 1 The polyethylene prepared using a Ziegler-Natta catalyst, XL1800 product by LG Chem, was used as Comparative Example 1.
Comparative Example 2 The polyethylene prepared using a Ziegler-Natta catalyst, 8100GX product by Lotte Chemical, was used as Comparative Example 2.
<Production of Crosslinked Polyethylene Pipe>
Example 4 100 g of polyethylene of Example 1 was mixed with 0.3 g of n-octadecy1-3-(3,5-di-tert.buty1-4-hydroxypheny1)-propionate (product name lrganox 1076, produced by BASF) as an antioxidant and 0.6 g of di-tert-butyl peroxide (product name: Trigonox B, produced by Akzo Nobel) as a crosslinking agent, and dispersed using a Henschel! Mixer (RPM 400, mixing time 15min, mix temp <40 C).
Subsequently, in order to produce the crosslinked polyethylene pipe, extrusion was performed with a Ram type extruder.
At this time, the pipe diameter of the extruder was set to 20mm, the thickness was set to 1.9mm, and the linear velocity during pipe extrusion was set to 2.2m/min. Temperature conditions were set to Body 130 C, Adaptor 180 C, Die - 240 C.
Date Recue/Date Received 2021-08-03 Example 5 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Example 2 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 2.1 m/min.
Example 6 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Example 3 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 2.1 m/min.
Comparative Example 3 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Comparative Example 1 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 1.8 m/min.
Comparative Example 4 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Comparative Example 2 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 1.8 m/min.
Comparative Example 5 The crosslinked polyethylene pipe was produced in the same manner as in Example 4, except that the polyethylene of Date Recue/Date Received 2021-08-03 Comparative Example 1 was used instead of the polyethylene of Example 1, and the linear velocity during pipe extrusion was set to 2.2 m/min.
<Experimental Example>
Evaluation of Physical Properties Physical properties of the polyethylene and the crosslinked polyethylene pipes produced in the Examples and Comparative Examples were evaluated by the following method.
(1) Weight average molecular weight (Mw) and molecular weight distribution (MWD, polydispersity index), GPC curve:
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer were measured using a gel permeation chromatography (GPC; produced by Waters Corp.), and the polydispersity index (PDI) was calculated by dividing the weight average molecular weight into the number average molecular weight.
Specifically, polyethylene sample was evaluated using a Waters PL-GPC220 instrument using a PLgel Mixed-B column (300 mm in length) from Polymer Laboratories, wherein an evaluation temperature was set to 160 C, 1,2,4-trichlorobenzene was used as a solvent, and a flow rate was set to 1 mL/min. In addition, a sample was prepared at a concentration of 10 mg/10 mL, and then supplied in an amount of 200 pL. A calibration curve formed by using a polystyrene standard was used to determine Mw and Mn values. The Date Recue/Date Received 2021-08-03 molecular weight of the polystyrene standard used was nine types of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 /
4,000,000 / 10,000,000.
(2) Melt Index (M121.6):
Measured according to the ASTM D1238 standard (Condition E, 190 C, 21.6 kg load).
(3) Density: Measured according to the ASTM D792 standard.
(4) Log Mw (6.0): Through the GPO curve graph measured in the above (1), it was calculated by the ratio of the integration value in a region where the Log Mw value is 6.0 or more relative to the entire area (integration value) of the entire GPC curve graph.
(5) crosslinking rate (T90, min) The crosslinking rate was measured according to ASTM D
5289, and was evaluated by measuring the time T90 until it became 90% of the maximum torque when a vulcanization curve was measured at 180 C for 30 minutes by a vulcanization tester (equipment name: Premier MDR, produced by Alpha Technologies).
The vibrational motion at this time was performed at 1Hz.
It means that as the value of T90 is smaller, the crosslinking proceeds faster, and that as the value is large, the crosslinking proceeds more slowly.
At this time, the sample used in the experiment was prepared as follows. First, 100 g of polyethylene, 0.3 g of antioxidant (Irganox 1076), and 0.6 g of crosslinking agent (di-tert-butyl peroxide) were mixed, and then the soaking time was set to 6 hours or more. Then, Date Recue/Date Received 2021-08-03 the press device (device name: Presses Type E, produced by Collin) was used to perform a melt process at 140 C and 30 bar for 4 minutes, and then prepared into a 2T sheet for use.
(6) Linear velocity During pipe production, the length produced for 1 minute with the portion passing through the water bath was measured three times using a tape measure, and the average value was taken as the linear velocity (unit: m/min).
(6) Degree of crosslinking: Measured according to KS M ISO
10147.
[Table 1]
Crosslinked Example Example Example Comparative Comparative Comparative polyethylene 4 5 6 Example 3 Example 4 Example 5 Polyethylene Example Example Example Comparative Comparative Comparative 1 2 3 Example 1 Example 2 Example 1 Mn (g/mol) 45,000 36,000 49,000 53,900 52,000 53,900 Mw (g/mol) 284,000 248,000 219,000 221,000 231,000 221,000 MWD 6.2 6.8 4.6 3.9 4.1 3.9 M 121 6 2.0 4.0 2.9 2.0 1.5 2.0 (g/10mi) Density 0.948 0.948 0.948 0.948 0.945 0.948 (g/cm3) Date Recue/Date Received 2021-08-03 Log MW 7.6 6.2 4/ 3.2 3.5 3.2 6.0 (%)*
T90 (min) 8.9 9.4 9.9 10.2 10.5 10.2 Linear 2.2 2.1 2.1 1.8 1.8 2.2 velocity (m/min) Degree of 86 86 83 87 75 80 crosslinking (%) * the ratio of the integration value of the area where the log Mw value was 6.0 or more relative to the total integral value, in the GPC curve graph where the x-axis is log Mw and the y-axis is dw/dlogMw.
Referring to Table 1, the polyethylene of Examples 1 to 3 according to the present disclosure exhibited a high content of ultra-high molecular weight, with the ratio of the integration value of the area where the log Mw value was 6.0 or more to the total integral value being 4.5% or more in the GPC curve graph.
Therefore, despite the crosslinking reaction proceeds rapidly with the crosslinking rate (T90) of less than 10 minutes during crosslinking, and even though extrusion was performed at a high linear velocity of 2.0m/min or more, the degree of crosslinking was shown to be equal to or superior to that of Comparative Examples.
Date Recue/Date Received 2021-08-03
Claims (12)
1. A polyethylene which satisfies:
a density of 0.940 g/cm3 or more and 0.960 g/cm3 or less as measured according to ASTM D792;
a number average molecular weight (Mn) of 20,000 g/mol or more and 70,000 g/mol or less;
a weight average molecular weight (Mw) of 150,000 g/mol or more and 350,000 g/mol or less;
a melt index (MI21.6) of 1 g/lOmin or more and 10 g/lOmin or less as measured at a temperature of 190 C under a load of 21.6 kg according to ASTM D1238, and an integration value in a region where log Mw value is 6.0 or more, of 4.5% or more relative to the total integration value, in a GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw.
a density of 0.940 g/cm3 or more and 0.960 g/cm3 or less as measured according to ASTM D792;
a number average molecular weight (Mn) of 20,000 g/mol or more and 70,000 g/mol or less;
a weight average molecular weight (Mw) of 150,000 g/mol or more and 350,000 g/mol or less;
a melt index (MI21.6) of 1 g/lOmin or more and 10 g/lOmin or less as measured at a temperature of 190 C under a load of 21.6 kg according to ASTM D1238, and an integration value in a region where log Mw value is 6.0 or more, of 4.5% or more relative to the total integration value, in a GPC curve graph in which the x axis is log Mw and the y axis is dw/dlog Mw.
2. The polyethylene according to claim 1, wherein the integration value in a region where the log Mw value is 6.0 or more is 4.5 to 10% relative to the total integration value.
3. The polyethylene according to claim 1, wherein a polydispersity index (PDI, Mw/Mn) is 3.0 or more and 10.0 or less.
Date Recue/Date Received 2021-08-03
Date Recue/Date Received 2021-08-03
4. The polyethylene according to claim 1, wherein the polyethylene includes a first metallocene compound represented by the following Chemical Formula 1 ; and a second metallocene compound represented by the following Chemical Formula 3, and is prepared polymerizing an ethylene monomer in the presence of a hybrid metallocene catalyst in which a molar ratio between the first metallocene compound and the second metallocene compound is 20:1 to 5:1.
[Chemical Formula 1]
c1 "11,, in the Chemical Formula 1, Qi and Q2 are the same as or different from each other, and each independently represents hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
B is carbon, silicon, or germanium;
Mi is a Group 4 transition metal;
Xi and X2 are the same as or different from each other, and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C10 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
one of Ci and C2 is represented by the following Chemical Date Recue/Date Received 2021-08-03 Formula 2a or Chemical Formula 2b, and the other of C1 and C2 is represented by the following Chemical Formula 2c;
[Chemical Formula 2a]
[Chemical Formula 2b]
R2' R3' R8' R4v R7' N
R81 R9' R13' Rs' R10' R12' R, [Chemical Formula 2c]
R20 AO* R15 in the Chemical Formulas 2a, 2b and 2c, Date Recue/Date Received 2021-08-03 Ri to R21 and Ri' to R13' are the same as or different from each other, and each independently represents hydrogen, a halogen, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl .. group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, provided that at least one of R9 to R13 and R9' to R13' is a C1 to C20 haloalkyl group, [Chemical Formula 3]
ept in the Chemical Formula 3, M2 is a Group 4 transition metal;
Cpi and Cp2 are the same as or different from each other, and each independently represents any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl, one or more hydrogens of the cyclic group is each independently substituted with any one substituent selected among a C1 to 20 alkyl, a C1 to C20 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl; and X3 and X4 are the same as or different from each other, and each independently represents a halogen, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl.
Date Recue/Date Received 2021-08-03
[Chemical Formula 1]
c1 "11,, in the Chemical Formula 1, Qi and Q2 are the same as or different from each other, and each independently represents hydrogen, a halogen, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkoxyalkyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
B is carbon, silicon, or germanium;
Mi is a Group 4 transition metal;
Xi and X2 are the same as or different from each other, and each independently represents a halogen, a C1 to C20 alkyl group, a C2 to C10 alkenyl group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group;
one of Ci and C2 is represented by the following Chemical Date Recue/Date Received 2021-08-03 Formula 2a or Chemical Formula 2b, and the other of C1 and C2 is represented by the following Chemical Formula 2c;
[Chemical Formula 2a]
[Chemical Formula 2b]
R2' R3' R8' R4v R7' N
R81 R9' R13' Rs' R10' R12' R, [Chemical Formula 2c]
R20 AO* R15 in the Chemical Formulas 2a, 2b and 2c, Date Recue/Date Received 2021-08-03 Ri to R21 and Ri' to R13' are the same as or different from each other, and each independently represents hydrogen, a halogen, a C1 to C20 alkyl group, a C1 to C20 haloalkyl group, a C2 to C20 alkenyl group, a C1 to C20 alkylsilyl group, a C1 to C20 silylalkyl .. group, a C1 to C20 alkoxysilyl group, a C1 to C20 alkoxy group, a C6 to C20 aryl group, a C7 to C20 alkylaryl group, or a C7 to C20 arylalkyl group, provided that at least one of R9 to R13 and R9' to R13' is a C1 to C20 haloalkyl group, [Chemical Formula 3]
ept in the Chemical Formula 3, M2 is a Group 4 transition metal;
Cpi and Cp2 are the same as or different from each other, and each independently represents any one cyclic compound selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl, one or more hydrogens of the cyclic group is each independently substituted with any one substituent selected among a C1 to 20 alkyl, a C1 to C20 alkoxy, a C2 to C20 alkoxyalkyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl; and X3 and X4 are the same as or different from each other, and each independently represents a halogen, a C1 to C20 alkyl, a C2 to C10 alkenyl, a C6 to C20 aryl, a C7 to C20 alkylaryl, or a C7 to C20 arylalkyl.
Date Recue/Date Received 2021-08-03
5. The polyethylene according to claim 4, wherein Ri to R21 and Ri' to Ri3' in Chemical Formulas 2a, 2b and 2c each independently represents hydrogen, a halogen, a C1 to C20 alkyl group, or a C1 to C20 haloalkyl group, and at least one of R9 to R13 and R9' to Ri3' is a C1 to C20 haloalkyl group,
6. The polyethylene according to claim 4, wherein the first metallocene compound represented by Chemical Formula 1 is a 1 0 compound represented by the following Chemical Formula 1-1:
[Chemical Formula 1-1]
ZrCl2
[Chemical Formula 1-1]
ZrCl2
7. The polyethylene according to claim 4, wherein 1 5 the second metallocene compound represented by Chemical Formula 3 is represented by one of the following structural formulas:
Date Recue/Date Received 2021-08-03 * * *
= # = 0 .
>r,0 ).10 *
Cl2 ra2 ):ItC12 >1'0 = )"0 # >1.0 =
12 irC12 >1'0 =
---Ph 4.
411).
12 404.
CS
Date Recue/Date Received 2021-08-03 4.4'..0 Zr 7rCl2 12 e12 ' /
Date Recue/Date Received 2021-08-03 * * *
= # = 0 .
>r,0 ).10 *
Cl2 ra2 ):ItC12 >1'0 = )"0 # >1.0 =
12 irC12 >1'0 =
---Ph 4.
411).
12 404.
CS
Date Recue/Date Received 2021-08-03 4.4'..0 Zr 7rCl2 12 e12 ' /
8. A crosslinked polyethylene pipe produced by a crosslinking reaction of the polyethylene of claim 1, and a crosslinking agent.
9. The crosslinked polyethylene pipe according to claim 8, wherein the crosslinking agent comprises at least one selected from the group consisting of di-t-butyl peroxide (DTBP), dicumyl peroxide, di-t-amyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
10. The crosslinked polyethylene pipe according to claim 8, wherein a degree of crosslinking measured according to KS M ISO
10147 is 70% or more.
10147 is 70% or more.
11. The crosslinked polyethylene pipe according to claim 8, wherein the pipe is PE-Xa pipe.
12. The crosslinked polyethylene pipe according to claim 8, wherein the crosslinking rate (T90) measured according to ASTM D
5289 is 10 minutes or less.
Date Recue/Date Received 2021-08-03
5289 is 10 minutes or less.
Date Recue/Date Received 2021-08-03
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