CN101575430B - Polyethylene resin composition and laminating body formed therefrom - Google Patents
Polyethylene resin composition and laminating body formed therefrom Download PDFInfo
- Publication number
- CN101575430B CN101575430B CN2009101376764A CN200910137676A CN101575430B CN 101575430 B CN101575430 B CN 101575430B CN 2009101376764 A CN2009101376764 A CN 2009101376764A CN 200910137676 A CN200910137676 A CN 200910137676A CN 101575430 B CN101575430 B CN 101575430B
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- CN
- China
- Prior art keywords
- polyethylene
- cyclopentadienyl
- bases
- zirconium dichloride
- indenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims abstract description 70
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 66
- 238000010030 laminating Methods 0.000 title abstract description 28
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 64
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 64
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003475 lamination Methods 0.000 claims abstract description 29
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 25
- 239000000155 melt Substances 0.000 claims abstract 3
- 229920005678 polyethylene based resin Polymers 0.000 claims description 114
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 50
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- 238000002844 melting Methods 0.000 claims description 35
- 230000008018 melting Effects 0.000 claims description 35
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 22
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 229920001038 ethylene copolymer Polymers 0.000 claims description 18
- 239000005977 Ethylene Substances 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 150000001721 carbon Chemical group 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 79
- 238000001125 extrusion Methods 0.000 abstract description 23
- 238000012545 processing Methods 0.000 abstract description 3
- -1 polyethylenes Polymers 0.000 description 246
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 103
- 230000015572 biosynthetic process Effects 0.000 description 82
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 79
- 238000004519 manufacturing process Methods 0.000 description 76
- 235000010290 biphenyl Nutrition 0.000 description 59
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 58
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 57
- 239000000203 mixture Substances 0.000 description 55
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 53
- 238000003786 synthesis reaction Methods 0.000 description 45
- 238000011156 evaluation Methods 0.000 description 44
- 238000003825 pressing Methods 0.000 description 37
- 239000000047 product Substances 0.000 description 37
- NZDLIIBVQQCHBI-UHFFFAOYSA-L Cl[Zr]Cl.CC1=C[CH]C=C1 Chemical compound Cl[Zr]Cl.CC1=C[CH]C=C1 NZDLIIBVQQCHBI-UHFFFAOYSA-L 0.000 description 31
- 239000002245 particle Substances 0.000 description 31
- 238000001816 cooling Methods 0.000 description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000000465 moulding Methods 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 22
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 238000005469 granulation Methods 0.000 description 16
- 230000003179 granulation Effects 0.000 description 16
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 16
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 14
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 13
- 229910000077 silane Inorganic materials 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000000123 paper Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 11
- 230000008676 import Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 9
- 229910000271 hectorite Inorganic materials 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000012018 catalyst precursor Substances 0.000 description 7
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 7
- 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 7
- 229920001903 high density polyethylene Polymers 0.000 description 7
- 239000004700 high-density polyethylene Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 7
- MXBBZANARLXZLS-UHFFFAOYSA-L CC1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C=CC=C1 Chemical compound CC1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C=CC=C1 MXBBZANARLXZLS-UHFFFAOYSA-L 0.000 description 6
- FAJJYXYRMUZENM-UHFFFAOYSA-L [Cl-].[Cl-].[Zr++]C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].[Zr++]C1c2ccccc2-c2ccccc12 FAJJYXYRMUZENM-UHFFFAOYSA-L 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 5
- AJIIPJIKASDPKD-UHFFFAOYSA-N C1CCCCC1[SiH2]C1CCCCC1 Chemical compound C1CCCCC1[SiH2]C1CCCCC1 AJIIPJIKASDPKD-UHFFFAOYSA-N 0.000 description 5
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical class Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- JWJXHIUDZWMVOK-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=C(C)C2=C1C([Zr+2])C(C)=C2 Chemical compound [Cl-].[Cl-].CC1=CC=C(C)C2=C1C([Zr+2])C(C)=C2 JWJXHIUDZWMVOK-UHFFFAOYSA-L 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- MQUBEBJFHBANKV-UHFFFAOYSA-N di(propan-2-yl)silicon Chemical compound CC(C)[Si]C(C)C MQUBEBJFHBANKV-UHFFFAOYSA-N 0.000 description 5
- 239000002655 kraft paper Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- BCSGKKPVRAKXLL-UHFFFAOYSA-N ethyl(methyl)silane Chemical compound CC[SiH2]C BCSGKKPVRAKXLL-UHFFFAOYSA-N 0.000 description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- QRLBICHXRCOJDU-UHFFFAOYSA-N methyl(phenyl)silane Chemical compound C[SiH2]C1=CC=CC=C1 QRLBICHXRCOJDU-UHFFFAOYSA-N 0.000 description 4
- WWDGNWGYFNUCQB-UHFFFAOYSA-N methyl(propan-2-yl)silane Chemical compound C[SiH2]C(C)C WWDGNWGYFNUCQB-UHFFFAOYSA-N 0.000 description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- RFPMGSKVEAUNMZ-UHFFFAOYSA-N pentylidene Chemical group [CH2+]CCC[CH-] RFPMGSKVEAUNMZ-UHFFFAOYSA-N 0.000 description 4
- 230000000379 polymerizing effect Effects 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- JTMNOQKSQBSGPD-UHFFFAOYSA-L Cc1ccc(C)c2C(C=Cc12)[Zr](Cl)(Cl)C1C=CC=C1 Chemical compound Cc1ccc(C)c2C(C=Cc12)[Zr](Cl)(Cl)C1C=CC=C1 JTMNOQKSQBSGPD-UHFFFAOYSA-L 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- KSDKNNOXWAJRQC-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)C1=C(C=CC=2C3=CC=C(C=C3C(C12)[Zr+2])C(C)(C)C)C(C)(C)C Chemical compound [Cl-].[Cl-].C1(C=CC=C1)C1=C(C=CC=2C3=CC=C(C=C3C(C12)[Zr+2])C(C)(C)C)C(C)(C)C KSDKNNOXWAJRQC-UHFFFAOYSA-L 0.000 description 3
- JOCMWVUBEWGFIU-UHFFFAOYSA-L [Cl-].[Cl-].Cc1ccc-2c(c1)C([Zr++])c1cc(C)ccc-21 Chemical compound [Cl-].[Cl-].Cc1ccc-2c(c1)C([Zr++])c1cc(C)ccc-21 JOCMWVUBEWGFIU-UHFFFAOYSA-L 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005469 ethylenyl group Chemical group 0.000 description 3
- 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 3
- 125000006038 hexenyl group Chemical group 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 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 3
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 3
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004344 phenylpropyl group Chemical group 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- VMNDCBPWBMKDBI-UHFFFAOYSA-N silinane Chemical compound C1CC[SiH2]CC1 VMNDCBPWBMKDBI-UHFFFAOYSA-N 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical group [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- YZYMXOBVMCYLAX-UHFFFAOYSA-L CC1=CC2=C(C)C=CC=C2C1[Zr](Cl)Cl Chemical compound CC1=CC2=C(C)C=CC=C2C1[Zr](Cl)Cl YZYMXOBVMCYLAX-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229920006387 Vinylite Polymers 0.000 description 2
- QTIYNLOLXYUIIH-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)=[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=C(C1=2)C1C=CC=C1)C(C)(C)C)C(C)(C)C Chemical compound [Cl-].[Cl-].C(C)(C)=[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=C(C1=2)C1C=CC=C1)C(C)(C)C)C(C)(C)C QTIYNLOLXYUIIH-UHFFFAOYSA-L 0.000 description 2
- CKFQJQXYCLQGRY-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C1=C2C=CC(C2=C(C=C1)C)[Zr+2] Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C1=C2C=CC(C2=C(C=C1)C)[Zr+2] CKFQJQXYCLQGRY-UHFFFAOYSA-L 0.000 description 2
- GOWACZLXHUFUNZ-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)C1=CC=CC=2C3=CC=CC=C3C(C1=2)[Zr+2] Chemical compound [Cl-].[Cl-].C1(C=CC=C1)C1=CC=CC=2C3=CC=CC=C3C(C1=2)[Zr+2] GOWACZLXHUFUNZ-UHFFFAOYSA-L 0.000 description 2
- ULBAZYNUJVBXTF-UHFFFAOYSA-L [Cl-].[Cl-].CC1(C=CC=C1)[Zr+2]C1C=CC2=CC=CC=C12 Chemical compound [Cl-].[Cl-].CC1(C=CC=C1)[Zr+2]C1C=CC2=CC=CC=C12 ULBAZYNUJVBXTF-UHFFFAOYSA-L 0.000 description 2
- VCOKPLHNHKEXIO-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=C(C)C2=C1C=CC2[Zr+2] Chemical compound [Cl-].[Cl-].CC1=CC=C(C)C2=C1C=CC2[Zr+2] VCOKPLHNHKEXIO-UHFFFAOYSA-L 0.000 description 2
- LKDKHGNCOQWROC-UHFFFAOYSA-L [Cl-].[Cl-].CC=1C=CC=C2C=CC(C12)[Zr+2] Chemical compound [Cl-].[Cl-].CC=1C=CC=C2C=CC(C12)[Zr+2] LKDKHGNCOQWROC-UHFFFAOYSA-L 0.000 description 2
- LJSGOOJPNHUWPL-UHFFFAOYSA-L [Cl-].[Cl-].[Zr++](C1C=Cc2ccccc12)C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].[Zr++](C1C=Cc2ccccc12)C1c2ccccc2-c2ccccc12 LJSGOOJPNHUWPL-UHFFFAOYSA-L 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- PMSZNCMIJVNSPB-UHFFFAOYSA-N bis(ethenyl)silicon Chemical compound C=C[Si]C=C PMSZNCMIJVNSPB-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- ZPFKRQXYKULZKP-UHFFFAOYSA-N butylidene Chemical group [CH2+]CC[CH-] ZPFKRQXYKULZKP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- KFDXCXLJBAVJMR-UHFFFAOYSA-N dibutylsilane Chemical compound CCCC[SiH2]CCCC KFDXCXLJBAVJMR-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/18—Bulk density
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Landscapes
- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
This invention relates to polyethylene resin composition and laminating body formed therefrom. The polyethylene resin composition includes: 1-50 weight% of low-density polyethylene (A) obtained by a high-pressure free radical polymerization method, whose density is 915-935kg/m<3>, the melt mass flow rate (MFR) measured at 2.16kg load (190 DEG C) is 0.5-5.0g/10minutes; and 99-50 weight% of polyethylene resin (B) satisfying the following conditions (a)-(c): (a) a density of 910-965kg/m<3>, (b) the long-chain branched-chain number C6 or above is 0.01 to 3.0 for every 1000 atoms carbon, (c) melt tension (MS190)(mN, 190 DEG C) and MFR (g/10 min) satisfies the formular (1): MS190> 22MFR<-0.88>, and the melt tension (MS160) (mN, 160 DEG C) and the MFR satisfies the formular (2): MS160> 110-110*log (MFR). The polyethylene resin composition has good processing, a lamination layer with excellent appearance can be obtained by extrusion lamination.
Description
Technical field
The layered product that the present invention relates to polyethylene resin composition and formed by it.In more detail, relate to the good polyethylene resin composition of outward appearance excellence by extruding the product that lamination obtains and processibility and the layered product formed by it.
Background technology
By extruding in the middle of the layered product that lamination process obtains, the layered product that at least one deck is polyethylene-based resin is used in the extensive use fields such as kraft paper packing, soft packaging, developing out paper supporter, tape, various containers.In the past, as the polyethylene-based resin used in these layered products, the main chain Low Density Polyethylene (LDPE) with excellent shaping processability that uses.But the density of LDPE is generally 0.918～0.925g/cm
3, the physical property, such as thermotolerance, rigidity, gas barrier property etc. that change with variable density are difficult, during use, are restricted.In addition, the forming speed of LDPE is fast, and then laminate thickness is when thin, and fused films is easily split, and under this condition, base material easily produces and engages badly, therefore, is difficult to obtain the product of stay in grade.On the other hand, the straight chain shaped polyethylenes such as straight chain shape Low Density Polyethylene (L-LDPE), straight chain shape high density polyethylene(HDPE) (HDPE), can density significantly be changed according to its short-chain branches number, but because shaping processability is poor, thereby be difficult to obtain layered product by extruding lamination process.So, thereby reported the mixture of straight chain shaped polyethylene and LDPE has been extruded to the method (for example, with reference to patent documentation 1～4) that lamination process obtains layered product.But the method produces thermal degradation when and easily produce foul smell in layered product in the mixed processes of polyethylene-based resin, thereby produce the uneven layered product that can not get surface smoothing of melting while making extrusion molding because the mixing of polyethylene-based resin is bad in addition.
In addition, reported and imported the long-chain side chain by changing the polymerizing catalyst of ethene in L-LDPE and HDPE, just can improve the technology (for example, with reference to patent documentation 5) of shaping processability without mixing LDPE.But the melting tension force of the polyethylene-based resin that uses these technology to obtain is still not enough, is difficult to stably carry out the extruding layer pressing formation.Therefore, the layered product of gained can't solve aforesaid problem as a result.
the prior art document
Patent documentation 1: Japanese kokai publication hei 6-65443 communique
Patent documentation 2: Japanese kokai publication hei 6-322189 communique
Patent documentation 3: Japanese kokai publication hei 7-92610 communique
Patent documentation 4: TOHKEMY 2000-73018 communique
Patent documentation 5: TOHKEMY 2006-43911 communique
Summary of the invention
the problem that invention will solve
The object of the invention is to, solve the problem of above-mentioned such prior art, the polyethylene resin composition that outward appearance is excellent and processibility is good by extruding the product that lamination obtains and the layered product formed by it are provided.
for the method for dealing with problems
The result that the present invention is furtherd investigate is to achieve these goals found.That is, the invention provides a kind of polyethylene resin composition, it is characterized in that, it comprises: the density obtained by the high-pressure free radical polymerization is 915～935kg/m
3, the lower melt mass flow rate measured of 2.16kg load (190 ℃) (below, be called MFR.) be Low Density Polyethylene (A) 1～50 % by weight of 0.5～5.0g/10 minute; And polyethylene-based resin (B) 99～50 % by weight that meet the condition of following (a)～(c).
(a) density is 910～965kg/m
3,
(b) the long-chain side chain number of carbon number more than 6 be 0.01～3.0 of every 1000 carbon atom,
(c) at the melting tension force (MS of 190 ℃ of mensuration
190) (mN) and at the lower MFR (g/10 minute) measured of 2.16kg load (190 ℃) meet following formula (1)
MS
190＞22×MFR
-0.88(1)
And the melting tension force (MS 160 ℃ of mensuration
160) (mN) and at the lower MFR (g/10 minute) measured of 2.16kg load (190 ℃) meet following formula (2).
MS
160＞110-110×log(MFR)(2)
the effect of invention
The outward appearance of polyethylene resin composition of the present invention by the product extruding lamination and obtain is excellent and processibility is good, useful with resin as extruding lamination.
Embodiment
Below, the present invention is described in detail.
Form polyethylene resin composition, the Low Density Polyethylene that obtain by the high-pressure free radical polymerization (A) for lamination of extruding of the present invention, its density is 915～935kg/m
3scope.The not enough 915kg/m of density
3the time, self tackiness of film increases, and likely lumps.On the other hand, density surpasses 935kg/m
3, the fusing point of Low Density Polyethylene (A) is high, and low-temperature heat-sealing likely worsens.
The scope that the Low Density Polyethylene used in the present invention (A) is 0.5～5.0g/10 minute at the lower MFR measured of 2.16kg load (190 ℃), the more preferably scope of 0.7～3.0g/10 minute.MFR is in the time of not enough 0.5g/10 minute, and it is large that the load of the forcing machine while melt extruding becomes, and in addition, by extruding lamination, with polyethylene resin composition, the outward appearance for the layered product obtained in extruding lamination process likely worsens.On the other hand, MFR likely becomes large within 5.0g/10 minute, curve inwardly (neck in).
The Low Density Polyethylene used in the present invention (A) is at the melting tension force (MS of 160 ℃ of mensuration
160) be preferably 100mN more than, more preferably more than 150mN.Melting tension force is 100mN when above, and fused film during lamination process is stable, and processibility is good, and roller pollutes and reduce, and can obtain excellent spatter property.
The Low Density Polyethylene used in the present invention (A) can obtain by existing known high-pressure free radical polymerization, in scope of the present invention, suitably selects.
Forming the lamination of extruding of the present invention is 910kg/m by the density of the polyethylene-based resin (B) of polyethylene resin composition
3above, 965kg/m
3below.The not enough 910kg/m of density
3the time, the thermotolerance of gained layered product is non-constant likely.On the other hand, density surpasses 965kg/m
3the time, the curling of layered product likely becomes significantly.
Weight-average molecular weight (the M that the straight chain shaped polyethylene of the polyethylene-based resin used in the present invention (B) converts
w) more than 10000, below 1000000, be preferred.M
wless than 10000 or surpass at 1000000 o'clock, be difficult to carry out the extruding layer pressing formation, therefore, likely can not get layered product.
The MFR in the lower mensuration of 2.16kg load (190 ℃) of the polyethylene-based resin used in the present invention (B) is within 0.1～100g/10 minute, to be preferred.Not enough 0.1g/10 minute or while surpassing 100g/10 minute, carry out the extruding layer pressing formation significantly difficulty that becomes, therefore likely can not get layered product.
The long-chain side chain number of the polyethylene-based resin used in the present invention (B) is that every 1000 carbon atoms are more than 0.01, below 3.0.During 0.01 of less than, carry out the extruding layer pressing formation significantly difficulty that becomes, therefore, likely can not get layered product.In addition, surpass 3.0 poor layered products of mechanical property that likely become the vinylite layer.In addition, long-chain side chain number refer to by
13c-NMR measures the number of the side chain of detected hexyl above (carbon number is more than 6).
Melting the 190 ℃ of mensuration tension force MS of the polyethylene-based resin used in the present invention (B)
190and be the relation shown in following formula (1) at the lower MFR (g/10 minute, 190 ℃) measured of 2.16kg load (190 ℃) (mN):
MS
190＞22×MFR
-0.88(1)
Be preferably following formula (1) ' shown in relation:
MS
190＞30×MFR
-0.88(1)’
And then be preferably following formula (1) " shown in relation:
MS
190＞5+30×MFR
-0.88(1)”
While not meeting (1) formula, for example do not meet MS
190>22 * MFR
-0.88l-LDPE and HDPE, carry out the extruding layer pressing formation significantly difficulty that becomes, therefore, likely can not get layered product.
Melting the 160 ℃ of mensuration tension force MS of the polyethylene-based resin used in the present invention in addition, (B)
160(mN) and at the lower MFR (g/10 minute, 190 ℃) measured of 2.16kg load (190 ℃) meet the relation shown in following formula (2):
MS
160＞110-110×log(MFR)(2)
Be preferably and meet following formula (2) ' shown in relation:
MS
160＞130-110×log(MFR)(2)’
And then be preferably following formula (2) " shown in relation:
MS
160＞150-110×log(MFR)(2)”。
While not meeting (2) formula, for example do not meet MS
160l-LDPE and the HDPE of>110-110 * log (MFR), carry out the extruding layer pressing formation and become significantly difficult, therefore, likely can not get layered product.
The polyethylene-based resin (B) that meets aforementioned condition (a), (b), (c) used in the present invention, be preferably under the existence of macromonomer or with macromonomer synthetic in by vinyl polymerization resulting (being total to) polymkeric substance, wherein said macromonomer comprises polymerisable polymkeric substance or the multipolymer of alkene., it is following ethene (being total to) polymkeric substance, it is under the existence of following macromonomer, or synthetic with this macromonomer the time, by independent polymerising ethylene, the perhaps olefinic polymerization more than 3 and obtaining by ethene and carbon number, this macromonomer is that the end obtained by olefin polymerization has the olefin polymer of vinyl or the macromonomer that multipolymer forms, the end more preferably obtained by independent polymerising ethylene has the ethene polymers of vinyl, perhaps, olefin-copolymerization by ethene and carbon number more than the 3 and end that obtains has the macromonomer that the ethylene copolymer of vinyl forms, and, macromonomer
(d) number-average molecular weight (M
n) be more than 2000,
(e) weight-average molecular weight (M
w) and number-average molecular weight (M
n) ratio (M
w/ M
n) be 2.0～5.0.
The end used as macromonomer has the polymkeric substance of ethene of vinyl or end and has multipolymer vinyl, ethene and the alkene of carbon number more than 3, is recorded in TOHKEMY 2004-346304 communique, TOHKEMY 2005-248013 communique, TOHKEMY 2006-321991 communique, TOHKEMY 2007-169341 communique.
For example polyethylene-based resin (B) can be by under the existence of above-mentioned macromonomer, or with above-mentioned macromonomer synthetic the time, the catalyzer of the transistion metal compound shown in following general formula (4) [composition (i)] as principal constituent usingd in use, independent polymerising ethylene, or by ethene and carbon number, the method for the olefin-copolymerization more than 3 is manufactured.
General formula (4):
M in composition (i)
1for titanium atom, zirconium atom or hafnium atom, X
1for example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.
As X
1in the alkyl of carbon number 1～20, can enumerate for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, norbornene, phenyl, styryl, xenyl, naphthyl, tolyl, ethylphenyl, the propyl group phenyl, butyl phenyl, 3,5-dimethylphenyl, the diethyl phenyl, the dipropyl phenyl, the dibutyl phenyl, the phenylbenzene phenyl, trimethylphenyl, the triethyl phenyl, the tripropyl phenyl, the tributyl phenyl, benzyl, phenylethyl, phenyl propyl, phenyl butyl, diphenyl methyl, diphenyl-ethyl, diphenyl propyl, the phenylbenzene butyl, vinyl, propenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl etc.
In addition, the R in composition (i)
1meaned the substituent R in these formulas by following general formula (5), (6) or (7)
4for example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.
General formula (5):
General formula (6):
General formula (7):
As the R in composition (i)
1concrete example, can enumerate cyclopentadienyl, methyl cyclopentadienyl, the dimethyl cyclopentadienyl, the trimethylammonium cyclopentadienyl, the tetramethyl-ring pentadienyl, the ethyl cyclopentadienyl, the diethyl cyclopentadienyl, the triethyl cyclopentadienyl, the tetraethyl-cyclopentadienyl, the propyl group cyclopentadienyl, the dipropyl cyclopentadienyl, the tripropyl cyclopentadienyl, the tetrapropyl cyclopentadienyl, the butyl cyclopentadienyl, the dibutyl cyclopentadienyl, the tributyl cyclopentadienyl, tetrabutyl cyclopentadienyl, the benzyl ring pentadienyl, the phenylbenzene cyclopentadienyl, the naphthyl cyclopentadienyl, the methoxyl group cyclopentadienyl, the trimethyl silyl cyclopentadienyl, indenyl, the methyl indenyl, the dimethyl indenyl, the trimethylammonium indenyl, the tetramethyl-indenyl, the pentamethyl-indenyl, the hexamethyl indenyl, ethyl-indenyl, the diethyl indenyl, the triethyl indenyl, the tetraethyl-indenyl, five ethyl-indenyls, the Hexaethyl indenyl, the propyl group indenyl, the dipropyl indenyl, the tripropyl indenyl, the tetrapropyl indenyl, the pentapropyl indenyl, six propyl group indenyls, the butyl indenyl, the dibutyl indenyl, the tributyl indenyl, tetrabutyl indenyl, five butyl indenyls, six butyl indenyls, phenyl indenyl, the phenylbenzene indenyl, the benzo indenyl, the naphthyl indenyl, the methoxyl group indenyl, trimethyl silyl indenyl etc.
R in composition (i)
2meaned substituent R by following general formula (8)
5for example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.
General formula (8):
As the R shown in general formula (8)
2concrete example, can enumerate for example fluorenyl, methylfluorenyl, the dimethyl fluorenyl, the trimethylammonium fluorenyl, the tetramethyl-fluorenyl, the pentamethyl-fluorenyl, the hexamethyl fluorenyl, seven methylfluorenyl, the prestox fluorenyl, the ethyl fluorenyl, the diethyl fluorenyl, the triethyl fluorenyl, the tetraethyl-fluorenyl, five ethyl fluorenyls, the Hexaethyl fluorenyl, seven ethyl fluorenyls, the octaethyl fluorenyl, the propyl group fluorenyl, the dipropyl fluorenyl, the tripropyl fluorenyl, the tetrapropyl fluorenyl, the pentapropyl fluorenyl, six propyl group fluorenyls, seven propyl group fluorenyls, eight propyl group fluorenyls, the butyl fluorenyl, the dibutyl fluorenyl, the tributyl fluorenyl, tetrabutyl fluorenyl, five butyl fluorenyls, six butyl fluorenyls, seven butyl fluorenyls, eight butyl fluorenyls, the phenyl fluorenyl, the phenylbenzene fluorenyl, the benzyl fluorenyl, the dibenzyl fluorenyl, the benzo fluorenyl, the dimethylamino fluorenyl, two (dimethylamino) fluorenyl, the methoxyl group fluorenyl, dimethoxy fluorenyl etc.
In addition, the R in the formula (4) of expression composition (i)
1with R
2crosslinked crosslinking group R
3mean substituent R with following general formula (9)
6for example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.Y
1for the atom of periodic table of elements IVA family, specifically, can enumerate such as carbon atom, Siliciumatom, germanium atom, tin atom etc., wherein be preferably carbon atom, Siliciumatom etc., the integer that m is 1～5.
General formula (9):
As the concrete example of general formula (9), can enumerate for example methylene radical, ethidine, ethylidene, the propylidene base, propylidene, fourth fork base, butylidene, the pentylidene base, pentylidene, oneself pitches base, isopropylidene, the methylethyl methylene radical, the methyl-propyl methylene radical, the methyl butyl methylene radical, two (cyclohexyl) methylene radical, the aminomethyl phenyl methylene radical, the phenylbenzene methylene radical, phenyl (aminomethyl phenyl) methylene radical, two (aminomethyl phenyl) methylene radical, two (3,5-dimethylphenyl) methylene radical, two (trimethylphenyl) methylene radical, phenyl (ethylphenyl) methylene radical, two (ethylphenyl) methylene radical, two (diethyl phenyl) methylene radical, phenyl (propyl group phenyl) methylene radical, two (propyl group phenyl) methylene radical, two (dipropyl phenyl) methylene radical, phenyl (butyl phenyl) methylene radical, two (butyl phenyl) methylene radical, phenyl (naphthyl) methylene radical, two (naphthyl) methylene radical, phenyl (xenyl) methylene radical, two (xenyl) methylene radical, phenyl (trimethyl silyl phenyl) methylene radical, two (trimethyl silyl phenyl) methylene radical, two (pentafluorophenyl group) methylene radical, silane two bases (silanediyl), disilane two bases, three silane two bases, tetrasilane two bases, dimethylsilane two bases, two (dimethylsilane) two bases, diethylsilane two bases, dipropyl silane two bases, dibutyl silane two bases, diphenyl silane two bases, silacyclobutane two bases, Silinane two bases etc.
As the concrete compound shown in general formula (4), at M
1for zirconium atom, X
1for chlorine atom, crosslinking group R
3during for the phenylbenzene methylene radical, for example can enumerate phenylbenzene methylene radical (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2-methyl isophthalic acid-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-methyl isophthalic acid-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2,5-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3,4-dimethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2,3,4-trimethylammonium-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2,3,5-trimethylammonium-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3,4,5-trimethylammonium-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2,3,4,5-tetramethyl--1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-ethyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-propyl group-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-sec.-propyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-phenyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-trimethyl silyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-methyl isophthalic acid-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3,4-dimethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-ethyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-propyl group-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-sec.-propyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-phenyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-trimethyl silyl-1-cyclopentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (1-cyclopentadienyl) (2,7-diethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-methyl isophthalic acid-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-sec.-propyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-phenyl-1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (1-indenyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2-methyl isophthalic acid-indenyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-methyl isophthalic acid-indenyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (2-methyl isophthalic acid-indenyl) (2,7-, bis--tertiary butyl-9-fluorenyl) zirconium dichloride, phenylbenzene methylene radical (3-methyl isophthalic acid-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride etc.In addition, also can enumerate the X of above-mentioned transistion metal compound
1be replaced to the compound of fluorine atom, bromine atoms or iodine atom.In addition, also can enumerate the R of above-mentioned transistion metal compound
3be substituted by the compound of methylene radical, ethylidene, isopropylidene, aminomethyl phenyl methylene radical, dimethylsilane two bases, diphenyl silane two bases, silacyclobutane two bases, Silinane two bases.And then, also can enumerate the M of above-mentioned transistion metal compound
2be replaced to the compound of titanium atom or hafnium atom.These compounds also can be used in a plurality of mixing.
As take the catalyzer that composition (i) is principal constituent, but illustration is by contacting with active cocatalyst [composition (iii)] catalyzer obtained by composition (i).
As composition (iii), can all use known material, wherein particularly preferably clay mineral, clay mineral, aikyiaiurnirsoxan beta, ionic compound, Lewis acid, magnesium chloride, surface treated inorganic oxide or the inorganic halides etc. processed through organic compound.
When manufacturing preferred polyethylene-based resin (B), as the alkene of carbon number more than 3 with ethylene copolymer, but diene or the vinylbenzene such as the cyclic olefins such as alpha-olefin, norbornylene or norbornadiene, divinyl or Isosorbide-5-Nitrae-hexadiene such as illustration propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene or vinyl cycloalkane.In addition, also can mix above these alkene of 2 kinds uses.
Macromonomer refers to that end has the olefin polymer of vinyl, and the end that is preferably independent polymerising ethylene and obtains and the end that obtains has olefin-copolymerization more than 3 of the ethene polymers of vinyl or ethene and carbon number has the ethylene copolymer of vinyl.And then be preferably straight chain shape ethene polymers or the straight chain shape ethylene copolymer that end as described below has vinyl,, be derived from the side chain side chain in addition of the alkene of carbon number more than 3, every 1000 main chain mesomethylene carbon, 0.01 of short-chain branches less than and every 1000 main chain mesomethylene carbon such as methyl branch, ethyl branch, propyl group side chain, butyl side chain, amyl group side chain, the long-chain side chain (
13the above side chain of detected hexyl during C-NMR measures) 0.01 of less than, end has straight chain shape ethene polymers or the straight chain shape ethylene copolymer of vinyl.
During macromonomer synthetic, as the alkene of carbon number more than 3 with ethylene copolymer, but diene or the vinylbenzene such as the cyclic olefins such as alpha-olefin, norbornylene or norbornadiene, divinyl or Isosorbide-5-Nitrae-hexadiene such as illustration propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene or vinyl cycloalkane.In addition, also can mix above these alkene of 2 kinds uses.
While as macromonomer, using end to there is the ethene polymers of vinyl or ethylene copolymer that end has vinyl, (D) number-average molecular weight (M that its straight chain shaped polyethylene converts
n) be, more than 2000, to be preferably more than 3000, and then be preferably more than 5000.M
n<2000 o'clock, become and do not meet formula (1) and/or formula (2), and carry out the extruding layer pressing formation significantly difficulty that becomes, therefore, likely can not get layered product.In addition, (E) weight-average molecular weight (M
w) and number-average molecular weight (M
n) ratio (M
w/ M
n) be 2.0～5.0, be preferably 2.0～4.0 and then be preferably 2.0～3.5.M
w/ M
n, likely become the layered product of intensity difference of the mechanics of vinylite layer at>5.0 o'clock.In addition, M
w/ M
n<2.0 o'clock, become and be difficult to carry out the extruding layer pressing formation, therefore, likely can not get layered product.
Manufacture method about the macromonomer in the present invention is not particularly limited, and can use the method for putting down in writing in for example TOHKEMY 2005-281676 communique, TOHKEMY 2006-28326 communique, TOHKEMY 2006-315999 communique, TOHKEMY 2007-169340 communique, TOHKEMY 2007-246433 communique, TOHKEMY 2008-50278 communique to manufacture.
Manufacture method as concrete macromonomer, for example can use and take the catalyzer that the transistion metal compound shown in following general formula (10) [composition (ii)] is principal constituent, manufacture by the method for independent polymerising ethylene or ethene and the olefin-copolymerization of carbon number more than 3.
General formula (10):
M in composition (ii)
2for titanium atom, zirconium atom or hafnium atom, X
2for example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.
As X
2in the alkyl of carbon number 1～20, can enumerate for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, norbornene, phenyl, styryl, xenyl, naphthyl, tolyl, ethylphenyl, the propyl group phenyl, butyl phenyl, 3,5-dimethylphenyl, the diethyl phenyl, the dipropyl phenyl, the dibutyl phenyl, the phenylbenzene phenyl, trimethylphenyl, the triethyl phenyl, the tripropyl phenyl, the tributyl phenyl, benzyl, phenylethyl, phenyl propyl, phenyl butyl, diphenyl methyl, diphenyl-ethyl, diphenyl propyl, the phenylbenzene butyl, vinyl, propenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl etc.
R in composition (ii)
7and R
8with following general formula (11), (12) or (13), mean, these can be identical or different separately, with M
2form sandwich structure.R in general formula (11), (12) or (13)
10for example independent separately is the alkyl of hydrogen atom, halogen atom, carbon number 1～20.
General formula (11):
General formula (12):
General formula (13):
As the R in general formula (11), (12) or (13)
10the alkyl of carbon number 1～20, can exemplify for example methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, norbornene, phenyl, styryl, xenyl, naphthyl, tolyl, ethylphenyl, the propyl group phenyl, butyl phenyl, 3,5-dimethylphenyl, the diethyl phenyl, the dipropyl phenyl, the dibutyl phenyl, the phenylbenzene phenyl, trimethylphenyl, the triethyl phenyl, the tripropyl phenyl, the tributyl phenyl, benzyl, phenylethyl, phenyl propyl, phenyl butyl, diphenyl methyl, diphenyl-ethyl, diphenyl propyl, the phenylbenzene butyl, vinyl, propenyl, butenyl, butadienyl, pentenyl, pentadienyl, hexenyl, hexadienyl etc.
As the R in general formula (10)
7and R
8concrete group, can enumerate for example cyclopentadienyl, methyl cyclopentadienyl, the dimethyl cyclopentadienyl, the trimethylammonium cyclopentadienyl, the tetramethyl-ring pentadienyl, the ethyl cyclopentadienyl, the diethyl cyclopentadienyl, the triethyl cyclopentadienyl, the tetraethyl-cyclopentadienyl, the propyl group cyclopentadienyl, the dipropyl cyclopentadienyl, the tripropyl cyclopentadienyl, the tetrapropyl cyclopentadienyl, the butyl cyclopentadienyl, the dibutyl cyclopentadienyl, the tributyl cyclopentadienyl, tetrabutyl cyclopentadienyl, the benzyl ring pentadienyl, the phenylbenzene cyclopentadienyl, the naphthyl cyclopentadienyl, the methoxyl group cyclopentadienyl, the trimethyl silyl cyclopentadienyl, indenyl, the methyl indenyl, the dimethyl indenyl, the trimethylammonium indenyl, the tetramethyl-indenyl, the pentamethyl-indenyl, the hexamethyl indenyl, ethyl-indenyl, the diethyl indenyl, the triethyl indenyl, the tetraethyl-indenyl, five ethyl-indenyls, the Hexaethyl indenyl, the propyl group indenyl, the dipropyl indenyl, the tripropyl indenyl, the tetrapropyl indenyl, the pentapropyl indenyl, six propyl group indenyls, the butyl indenyl, the dibutyl indenyl, the tributyl indenyl, tetrabutyl indenyl, five butyl indenyls, six butyl indenyls, phenyl indenyl, the phenylbenzene indenyl, the benzo indenyl, the naphthyl indenyl, the methoxyl group indenyl, trimethyl silyl indenyl etc.
In addition, the R in general formula (10)
7, R
8the crosslinking group R be cross-linked to form
9with following general formula (14), (15) or (16), mean, in these formulas (14), (15), (16), substituent R
11for example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.In addition, Y
2for the atom of periodic table of elements IVA family, specifically, can enumerate such as carbon atom, Siliciumatom, germanium atom, tin atom etc., wherein be preferably carbon atom, Siliciumatom, the integer that n is 1～5.
General formula (14):
General formula (15):
General formula (16):
R as general formula (14), (15) or (16)
11in the alkyl of carbon number 1～20, for example can enumerate and R
10in the identical material of alkyl of carbon number 1～20.
As the concrete example of general formula (14), can enumerate for example methylene radical, ethidine, ethylidene, the propylidene base, propylidene, fourth fork base, butylidene, the pentylidene base, pentylidene, oneself pitches base, isopropylidene, the methylethyl methylene radical, the methyl-propyl methylene radical, the methyl butyl methylene radical, two (cyclohexyl) methylene radical, the aminomethyl phenyl methylene radical, the phenylbenzene methylene radical, phenyl (aminomethyl phenyl) methylene radical, two (aminomethyl phenyl) methylene radical, two (3,5-dimethylphenyl) methylene radical, two (trimethylphenyl) methylene radical, phenyl (ethylphenyl) methylene radical, two (ethylphenyl) methylene radical, two (diethyl phenyl) methylene radical, phenyl (propyl group phenyl) methylene radical, two (propyl group phenyl) methylene radical, two (dipropyl phenyl) methylene radical, phenyl (butyl phenyl) methylene radical, two (butyl phenyl) methylene radical, phenyl (naphthyl) methylene radical, two (naphthyl) methylene radical, phenyl (xenyl) methylene radical, two (xenyl) methylene radical, phenyl (trimethyl silyl phenyl) methylene radical, two (trimethyl silyl phenyl) methylene radical, two (pentafluorophenyl group) methylene radical, silane two bases, disilane two bases, three silane two bases, tetrasilane two bases, dimethylsilane two bases, two (dimethylsilane) two bases, diethylsilane two bases, dipropyl silane two bases, dibutyl silane two bases, diphenyl silane two bases, silacyclobutane two bases, Silinane two bases, divinyl silane two bases, diallylsilane two bases, (methyl) (vinyl) silane two bases, (allyl group) (methyl) silane two bases etc.
As the concrete example of general formula (15), for example can enumerate 1,1,3,3-tetramethyl disiloxane-1,3-bis-bases, 1,1,3,3-tetraethyl-sily oxide-1,3-bis-bases, 1,1,3,3-tetra isopropyl disiloxane-1,3-bis-bases, 1,1,3,3-tetraphenyl sily oxide-1,3-bis-bases etc.
As the concrete example of general formula (16), for example can enumerate 1,1-dimethyl-1-sila ethane-1,2-bis-bases, 1,1-diethyl-1-sila ethane-1,2-bis-bases, 1,1-di-isopropyl-1-sila ethane-1,2-bis-bases, 1,1-phenylbenzene-1-sila ethane-1,2-bis-bases etc.
As the concrete compound shown in the general formula used in the present invention (10), at M
2for zirconium atom, X
2for the chlorine atomic time, can enumerate for example di-2-ethylhexylphosphine oxide (cyclopentadienyl group) zirconium dichloride, two (cyclopentadienyl group) zirconium dichlorides of isopropylidene, (methyl) (phenyl) di-2-ethylhexylphosphine oxide (cyclopentadienyl group) zirconium dichloride, diphenyl di-2-ethylhexylphosphine oxide (cyclopentadienyl group) zirconium dichloride, ethylenebis (cyclopentadienyl group) zirconium dichloride, di-2-ethylhexylphosphine oxide (methyl cyclopentadienyl) zirconium dichloride, two (methyl cyclopentadienyl) zirconium dichlorides of isopropylidene, (methyl) (phenyl) di-2-ethylhexylphosphine oxide (methyl cyclopentadienyl) zirconium dichloride, diphenyl di-2-ethylhexylphosphine oxide (methyl cyclopentadienyl) zirconium dichloride, ethylenebis (methyl cyclopentadienyl) zirconium dichloride, methylene (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, isopropylidene (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, diphenyl methylene (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, ethylidene (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, di-2-ethylhexylphosphine oxide (2,4-dimethyl cyclopentadienyl group) zirconium dichloride, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of isopropylidene, (methyl) (phenyl) di-2-ethylhexylphosphine oxide (2,4-dimethyl cyclopentadienyl group) zirconium dichloride, diphenyl di-2-ethylhexylphosphine oxide (2,4-dimethyl cyclopentadienyl group) zirconium dichloride, ethylenebis (2,4-dimethyl cyclopentadienyl group) zirconium dichloride, methylene (cyclopentadienyl group) (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl group) (indenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl group) (indenyl) zirconium dichloride, diphenyl methylene (cyclopentadienyl group) (indenyl) zirconium dichloride, ethylidene (cyclopentadienyl group) (indenyl) zirconium dichloride, two (cyclopentadienyl group) zirconium dichlorides of dimethylsilane two bases, two (cyclopentadienyl group) zirconium dichlorides of diethylsilane two bases, two (cyclopentadienyl group) zirconium dichlorides of two (n-pro-pyl) silane, two bases, two (cyclopentadienyl group) zirconium dichlorides of diisopropyl silane two bases, two (cyclopentadienyl group) zirconium dichlorides of dicyclohexyl silane two bases, two (cyclopentadienyl group) zirconium dichlorides of diphenyl silane two bases, two (cyclopentadienyl group) zirconium dichlorides of two (p-methylphenyl) silane, two bases, two (cyclopentadienyl group) zirconium dichlorides of divinyl silane two bases, two (cyclopentadienyl group) zirconium dichlorides of diallylsilane two bases, two (cyclopentadienyl group) zirconium dichlorides of (methyl) (vinyl) silane two bases, two (cyclopentadienyl group) zirconium dichlorides of (pi-allyl) (methyl) silane two bases, two (cyclopentadienyl group) zirconium dichlorides of (ethyl) (methyl) silane two bases, two (cyclopentadienyl group) zirconium dichlorides of (methyl) (n-pro-pyl) silane two bases, two (cyclopentadienyl group) zirconium dichlorides of (methyl) (isopropyl) silane two bases, (cyclohexyl) (methyl) two (cyclopentadienyl group) zirconium dichloride, two (cyclopentadienyl group) zirconium dichlorides of (methyl) (phenyl) silane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of diethylsilane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of two (n-pro-pyl) silane, two bases, two (methyl cyclopentadienyl) zirconium dichlorides of diisopropyl silane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of dicyclohexyl silane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of diphenyl silane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of (ethyl) (methyl) silane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of (methyl) (n-pro-pyl) silane two bases, two (methyl cyclopentadienyl) zirconium dichlorides of (methyl) (isopropyl) silane two bases, (cyclohexyl) (methyl) two (methyl cyclopentadienyl) zirconium dichloride, two (methyl cyclopentadienyl) zirconium dichlorides of (methyl) (phenyl) silane two bases, dimethylsilane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, diethylsilane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, two (n-pro-pyl) silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, diisopropyl silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, dicyclohexyl silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, diphenyl silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, (ethyl) (methyl) silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, (methyl) (n-pro-pyl) silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, (methyl) (isopropyl) silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, (cyclohexyl) (methyl) (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, (methyl) (phenyl) silane two bases (cyclopentadienyl group) (methyl cyclopentadienyl) zirconium dichloride, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of dimethylsilane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of diethylsilane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of two (n-pro-pyl) silane, two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of diisopropyl silane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of dicyclohexyl silane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of diphenyl silane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of (ethyl) (methyl) silane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of (methyl) (n-pro-pyl) silane two bases, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of (methyl) (isopropyl) silane two bases, (cyclohexyl) (methyl) two (2,4-dimethyl cyclopentadienyl group) zirconium dichloride, two (2, the 4-dimethyl cyclopentadienyl group) zirconium dichlorides of (methyl) (phenyl) silane two bases, dimethylsilane two bases (cyclopentadienyl group) (indenyl) zirconium dichloride, diethylsilane two bases (cyclopentadienyl group) (indenyl) zirconium dichloride, two (n-pro-pyl) silane two bases (cyclopentadienyl group) (indenyl) zirconium dichloride, diisopropyl silane two bases (cyclopentadienyl group) (indenyl) zirconium dichloride, dicyclohexyl silane two bases (cyclopentadienyl group) (indenyl) zirconium dichloride, diphenyl silane two bases (cyclopentadienyl group) (indenyl) zirconium dichloride, dimethylsilane two bases (2-methyl cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilane two bases (3-methyl cyclopentadienyl) (indenyl) zirconium dichloride, dimethylsilane two bases (3-isopropyl cyclopentadienyl group) (indenyl) zirconium dichloride, dimethylsilane two bases (2,3-dimethyl cyclopentadienyl group) (indenyl) zirconium dichloride, dimethylsilane two bases (2,4-dimethyl cyclopentadienyl group) (indenyl) zirconium dichloride, dimethylsilane two bases (2,3,4-trimethyl cyclopentadienyl group) (indenyl) zirconium dichloride, dimethylsilane two bases (2,3,5-trimethyl cyclopentadienyl group) (indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (7-ethyl-indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (7-phenyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2,7-dimethyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (4,7-dimethyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2-methoxyl group-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2-dimethylamino-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2-trimethyl silyl-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (tetramethyl-ring pentadienyl) (7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (tetramethyl-ring pentadienyl) (2,7-dimethyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (4-isopropyl-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (4-phenyl-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (4-methoxyl group-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (4-dimethylamino-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (4-trimethyl silyl-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2,4,7-trimethyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (3,4,7-trimethyl indenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl group) (2,3,4,7-tetramethyl indenyl) zirconium dichloride, dimethylsilane two bases (3,4-dimethyl cyclopentadienyl group) (2,4,7-trimethyl indenyl) zirconium dichloride, dimethylsilane two bases (two (trimethyl silyl) cyclopentadienyl groups of 3,4-) (2,4,7-trimethyl indenyl) zirconium dichloride, dimethylsilane two bases (tetramethyl-ring pentadienyl) (4,7-dimethyl indenyl) zirconium dichloride, dimethylsilane two bases (tetramethyl-ring pentadienyl) (4-phenyl-7-methyl indenyl) zirconium dichloride, dimethylsilane two bases (tetramethyl-ring pentadienyl) (2,4,7-trimethyl indenyl) zirconium dichloride, dimethylsilane two bases (tetramethyl-ring pentadienyl) (2,4,7-trimethyl indenyl) zirconium dichloride, (1,1,3,3-tetramethyl disiloxane-1,3-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1,3,3-tetra isopropyl disiloxane-1,3-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1,3,3-tetraphenyl disiloxane-1,3-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1-dimethyl-1-sila ethane-1,2-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1-diisopropyl-1-sila ethane-1,2-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1-diphenyl-1-sila ethane-1,2-bis-bases-bicyclic pentadiene) zirconium dichloride, (propane-1,3-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1,3,3-tetramethyl propane-1,3-bis-bases-bicyclic pentadiene) zirconium dichloride, (2,2-dimethylpropane-1,3-bis-bases-bicyclic pentadiene) zirconium dichloride, (butane-Isosorbide-5-Nitrae-bis-bases-bicyclic pentadiene) zirconium dichloride, (pentane-1,5-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1,2,2-tetramethyl disilane-1,2-bis-bases-bicyclic pentadiene) zirconium dichloride, (1,1,2,2-tetraphenyl disilane-1,2-bis-bases-bicyclic pentadiene) zirconium dichloride etc.In addition, also can enumerate the X of above-mentioned transistion metal compound
1be substituted by the compound of fluorine atom, bromine atoms or iodine atom.And then, also can enumerate the M of above-mentioned transistion metal compound
2be substituted by the compound of titanium atom or hafnium atom.These compounds also can be used a plurality of mixing.
As take the catalyzer that the composition (ii) shown in formula (10) is principal constituent, can enumerate composition (ii) is contacted to the catalyzer obtained with active cocatalyst composition (iii).As the concrete example of composition (iii), about take the catalyzer that composition (i) is principal constituent, can enumerate with and the same material of the aforementioned composition (iii) that is used in combination of composition (i).
The concrete manufacture method of polyethylene-based resin of the present invention (B) is not particularly limited, can enumerate: (1) is used and be take catalyzer that composition (ii) be principal constituent by after ethene and any olefinic polymerization synthetic macromolecule monomer of carbon number more than 3, under the existence of gained macromonomer, use and take catalyzer that composition (i) be principal constituent by ethene and the method for the olefinic polymerization manufacture polyethylene-based resin (B) of carbon number more than 3 arbitrarily; And (2) used and take catalyzer that composition (i) and composition (ii) be principal constituent by ethene and any olefinic polymerization of carbon number more than 3, the method for manufacture polyethylene-based resin (B) in macromonomer synthetic.
Polyethylene-based resin (B) is introduced as comonomer by the part of the macromonomer that will use composition (ii) and obtain, thereby becomes the resin that its part has the long-chain side chain.When the molecular weight of general macromonomer is low, it is many that the macromonomer number becomes, and therefore, the quantitative change of long-chain side chain is many, excellent in workability, but number-average molecular weight step-down, physical strength step-down.On the other hand, when the molecular weight of macromonomer is high, physical strength uprises, but does not generate the long-chain side chain, and processibility reduces.Polyethylene-based resin of the present invention (B) is preferably has the long-chain branched structure and number-average molecular weight is high, molecular weight distribution is narrow polyethylene-based resin (B), has excellent processibility and physical strength high.
The manufacture of polyethylene-based resin of the present invention (B) can be undertaken by any means of vapour phase polymerization, slurry polymerization, solution polymerization, when carrying out with slurry polymerization, can manufacture the polyethylene-based resin of excellent particle form.
In the manufacture of the synthetic and polyethylene-based resin (B) of macromonomer, the polymerizing conditions such as polymerization temperature, polymerization time, polymerization pressure, monomer concentration are not particularly limited, polymerization temperature is-100～120 ℃, while considering productivity preferably at 20～120 ℃ and then preferably carry out the scope of 60～120 ℃.Polymerization time carries out the scope of 10 seconds～20 hours usually, and polymerization pressure can carry out in the scope of normal pressure～300MPa.In addition, when polymerization, also can use hydrogen etc. to carry out the adjusting of molecular weight.Polymerization can be used any method of intermittent type, semi continuous, continous way to carry out, and also can change polymerizing condition and divide more than 2 stages and carry out.
The polyethylene-based resin (B) that meets the condition of above-mentioned (a)～(c) can creating conditions or the change of the small-scale of Factors and operation respectively arbitrarily according to embodiment described later.Concrete example to Factors change describes, can be according to the structure of used composition (ii) and composition (i), with respect to the kind of the amount of the composition (i) of composition (ii), the co-catalyst component used etc., amount, the polymerizing conditions such as amount of comonomers that add of the condition relevant with catalyst component, polymerization temperature, ethylene partial pressure, the hydrogen equimolecular quantity adjusting agent that coexists are controlled respectively and operated.In addition, also can further with multi-stage polymeric, combine to enlarge the scope of physical property.
More particularly, such as can be by reducing ethylene partial pressure, reduce the comonomer addition, the structure etc. that changes composition (ii) reduces the terminal ethylenyl groups number.In addition, melting tension force can prop up chain length by the structure of change composition (ii), the structure that increases terminal ethylenyl groups number, change composition (i), reduction ethylene partial pressure, increase long-chain side chain number, increase long-chain, change amount, increase M with respect to the composition (i) of composition (ii)
w/ M
ndeng increasing.And then, mobile activation energy (E
a) can prop up by structure, terminal ethylenyl groups number, the structure of composition (i), ethylene partial pressure, long-chain side chain number, the long-chain of composition (ii) chain length, control with respect to the amount of the composition (i) of composition (ii).
Mixed the Low Density Polyethylene that meets above-mentioned condition (A) of specified quantitative and the polyethylene resin composition of polyethylene-based resin (B), the outward appearance by extruding the product that lamination obtains is excellent and processibility is good.Polyethylene resin composition of the present invention comprises: 1～50 % by weight, be preferably 1～30 % by weight and then be preferably 1～20 % by weight Low Density Polyethylene (A), 99～50 % by weight, be preferably 99～70 % by weight and then be preferably 99～80 % by weight polyethylene-based resins (B).During use level less than 1 % by weight of Low Density Polyethylene (A), likely be difficult to stably carry out the extruding layer pressing formation.On the other hand, when the use level of Low Density Polyethylene (A) surpasses 50 % by weight, likely be difficult to the attenuate laminate thickness.
The density of polyethylene resin composition of the present invention is preferably 915～965kg/m
3, and then be preferably 920～960kg/m
3.Density is 915～965kg/m
3scope the time, can take into account thermotolerance and the stopping property of laminate product.
Polyethylene resin composition of the present invention preferably is 3.0～30.0g/10 minute and then is preferably 4.0～20g/10 minute at the lower MFR measured of 2.16kg load (190 ℃).During scope that MFR is 3.0～30.0g/10 minute, but thereby the attenuate laminate thickness is stably carried out the extruding layer pressing formation.
Polyethylene resin composition of the present invention is preferably at the melting tension force (MS of 160 ℃ of mensuration
160) for more than 30mN and then more than being preferably 40mN.Melting tension force (MS
160) be 30mN when above, can stably carry out the extruding layer pressing formation.
Form the lamination of extruding of the present invention and can be respectively a kind or the above mixture of 2 kinds with Low Density Polyethylene (A), the polyethylene-based resin (B) of polyethylene resin composition.
Polyethylene resin composition of the present invention can mix Low Density Polyethylene (A) and polyethylene-based resin (B) dry type to modulate, carry out by the existing known method such as single screw extrusion machine, twin screw extruder, kneader, banbury mixers the composition that melting mixing can obtain stay in grade, therefore preferably.Consider from the productivity aspect in the middle of these, be generally the method for use single screw extrusion machine or twin screw extruder melting mixing, granulation.
Can coordinate the known additives such as the inorganic fillers such as heat-resisting stabilizing agent, weather-proof stablizer, antistatic agent, antifogging agent, anti-caking agent, the agent of skidding, lubricant, nucleator, pigment, tackifier, carbon black, talcum, glass powder, glass fibre or toughener, organic filler or toughener, fire retardant, neutron screening agent in polyethylene-based resin of the present invention.In addition, also can mix with other thermoplastic resins use.As these examples, can enumerate resin of tackification, wax, HDPE, L-LDPE, polypropylene, poly-1-butylene, poly--4-methyl-1-pentene, ethylene vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polystyrene or these maleic anhydride grafts etc.
Layered product of the present invention can obtain by utilizing extruding layer pressing formation method will form the polyethylene-based resin composition lamination of one deck at least and/or be applied on various base materials.Extruding layer pressing formation method can be any of single entry laminating machine, series connection laminating machine, co-extrusion laminating machine, sandwich of layers press, is not particularly limited.In addition, while being extruded lamination process, for the good layered product of the connectivity that obtains base material and polyethylene-based resin layer, preferably at the temperature of 250～350 ℃ from die extrusion.
In addition, the face that the fused films of polyethylene-based resin composition at least contacts with base material can be by air or oxidation by ozone gas.While utilizing air to carry out oxidizing reaction, at the temperature more than 270 ℃, from die extrusion, being preferred, in addition, while utilizing ozone gas to carry out oxidizing reaction, is preferred extruding more than 250 ℃.In addition, as the treatment capacity of ozone gas, from every 1m of die extrusion
2film is more than 0.5mg, to be preferred.In addition, in order to improve the connectivity with base material, can carry out to the junction surface of base material the known surface treatments such as anchor coating agent processing, Corona discharge Treatment, frame processing, plasma treatment.
As base material, can enumerate synthesising macromolecule copolymer film and thin slice, spin cloth, non-woven fabrics, tinsel, stationery, cellulose film etc.The formed film such as the synthesising macromolecule copolymer such as polyethylene terephthalate, polymeric amide, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene and thin slice etc.And then, these high molecular polymer films and thin slice and then can be the material that deposition of aluminum, deposition of aluminium oxide, deposition of silica form.In addition, these high molecular polymer films and thin slice also can be used the printing such as polyurethane series China ink to form.As tinsel, but illustration aluminium foil, Copper Foil etc., and in addition, stationery can be enumerated the paperboards such as kraft paper, extensible paper, vellum, glassine paper, cup body paper and developing out paper body paper etc.
The toilet articles such as backing layer, developing out paper supporter, paper-made vessel and lid, paper ware, release paper and the demoulding tape of the drug packagings such as beverage diet product packing, medicine, transfusion band such as desiccating food products, soup, sauce, salted vegetables, sauce, beverage such as layered product of the present invention can be littlely graing a bite, instant hand-pulled noodles, shampoo, makeup, diaper, easily in the wide scope such as dissociative film, half distillation bag made of paper, as film, container, tape, supporter, use.
embodiment
For the present invention, be specifically described by the following examples, but the present invention is not limited to this.
Each physical property of polyethylene-based resin in synthesis example, embodiment and comparative example is measured by method shown below.
<molecular weight, molecular weight distribution >
Weight-average molecular weight (M
w) and number-average molecular weight (M
n) by gel permeation chromatograph (GPC), measure.The HLC-8121GPC/HT that uses TOSOH Co., Ltd to manufacture as the GPC device, TSK gelGMHhr-H (20) HT, the column temperature of using TOSOH Co., Ltd to manufacture as post are set as 140 ℃, elutriant and use 1,2,4-trichlorobenzene to measure.Measure the Concentration Modulation of test portion with 1.0mg/mL, inject 0.3mL and measure.The polystyrene test portion that the working curve of molecular weight is known with molecular weight is proofreaied and correct.In addition, M
wand M
nthe value converted as the straight chain shaped polyethylene is tried to achieve.
<long-chain side chain number >
The VNMRS-400 type nuclear magnetic resonance device that long-chain side chain number is used Varian to manufacture, pass through
13c-NMR measures the number of the above long-chain side chain of hexyl.Solvent is tetrachloroethane-d
2.As the number of every 1000 main chain mesomethylene carbon, by the following formula (4) of record in " Macromolecules " the 31st volume, No. 25,8677～8683 pages (1998), try to achieve.
Long-chain side chain number=IA
α/ (3 * IA
tot) (4)
[in formula, IA
αalpha-carbon peak (chemical shift: integrated intensity 34.6ppm), IA for the long-chain side chain more than hexyl
totintegrated intensity for the peak (30.0ppm) of main chain mesomethylene carbon.]
The VNMRS-400 type nuclear magnetic resonance device that the end structure of the polymkeric substance of vinyl end, saturated end etc. is used Varian to manufacture passes through
13c-NMR measures.Solvent is tetrachloroethane-d
2.Vinyl end number as every 1000 main chain mesomethylene carbon, (chemical shift: number 30ppm), try to achieve by the mean value at the peak by 114ppm, 139ppm.In addition, saturated end number equally the mean value at the peak by 32.3ppm, 22.9ppm, 14.1ppm try to achieve.Obtain the containing ratio Z (=X/ (X+Y) * 2) of vinyl end from this vinyl end number (X) and saturated end number (Y).
<density >
Density is measured by the density gradient tube method according to JIS K6760 (1995).
<MFR>
MFR measures under 190 ℃, 2.16kg load according to JIS K6760 (1995).
<melting tension force >
The polyethylene that is used for the mensuration of melting tension force (MS), using the IRGANOX1010 added in advance as heat-resisting stabilizing agent
tM(Ciba Specialty ChemicalsCorporation system) 1500ppm, IRGAFOS168
tMthe material that (Ciba SpecialtyChemicals Corporation system) 1500ppm forms, use Banbury mixer (Japan's essence mechanism is made made, trade(brand)name: Laboratory mill), under stream of nitrogen gas, 190 ℃, with rotating speed 30rpm mixing 3 minutes.Melting tension force (MS) at the capillary viscosimeter of cylinder diameter 9.55mm, (Japan's essence mechanism is made institute, trade(brand)name: measure by the mouth mould that pack into キ ヤ ピ ロ グ ラ Off) length (L) 8mm, diameter (D) 2.095mm, fluid inlet angle are 90 °.MS
160for being that 160 ℃, piston rotation perdurability are that 10mm/ minute, ratio of elongation are set as 47 by Temperature Setting, measure and receive necessary load (mN).MS
190for being that 190 ℃, piston rotation perdurability are that 10mm/ minute, ratio of elongation are set as 47 by Temperature Setting, measure and receive necessary load (mN).
<curve inwardly
Polyethylene resin composition is supplied to extruding layer press (the Musashino Kikai Co. of the screw rod with 90mm φ, Ltd. forcing machine manufacture), T die head from A/F 600mm at the temperature of 315 ℃ is extruded, the inbound pacing of base material is 200m/ minute, in the weight of paper, is 50g/m
2the kraft paper base material on according to extruding, resin composition for lamination is that 20 μ m thickness are while being extruded lamination, the difference of coating width T die openings width and polyethylene resin composition is as curving inwardly, measure this value.Now, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) compares that the little situation that curves inwardly is designated as zero, many situations are designated as *, identical situation is designated as △.
<minimum film thickness >
Polyethylene resin composition is supplied to extruding layer press (the Musashino Kikai Co. with 90mm φ screw rod, Ltd. forcing machine manufacture), T die head from A/F 600mm at the temperature of 315 ℃ is extruded, and the inbound pacing of base material is 200m/ minute, in the weight of paper, is 50g/m
2the kraft paper base material on according to extruding resin composition for lamination, be that 20 μ m thickness are extruded lamination., reduce discharge-amount, can not carry out the laminate thickness of extruding layer pressing formation of the above continous-stable of 100m as minimum film thickness, measure this value thereafter.Now, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) compares that situation that minimum film thickness is thin is designated as zero, thick situation is designated as *, identical situation is designated as △.
The outward appearance of<fused films >
Polyethylene resin composition is supplied to extruding layer press (the Musashino Kikai Co. of the screw rod with 90mm φ, Ltd. forcing machine manufacture), T die head from A/F 600mm at the temperature of 315 ℃ is extruded, the outward appearance of visual observation fused films.Now, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) compares that the good situation of outward appearance is designated as zero, bad situation is designated as *, identical situation is designated as △.
The pollution on<cooling roller surface >
Polyethylene resin composition is supplied to extruding layer press (the Musashino Kikai Co. of the screw rod with 90mm φ, Ltd. forcing machine manufacture), T die head from A/F 600mm at the temperature of 315 ℃ is extruded, the inbound pacing of base material is 20m/ minute, in the weight of paper, is 50g/m
2the kraft paper base material on according to extruding resin composition for lamination, be that 20 μ m thickness carry out continuous 500m extruding layer pressing formation.After laminating molding, measure the dirt settling on cooling roller surface.Now, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) compares that the good situation in cooling roller surface is designated as zero, bad situation is designated as *, identical situation is designated as △.In addition, cooling roller is used the Miller roller, and the roller cooling temperature is 45 ℃.
And then the manufacture of the modulation of modification hectorite, the modulation of catalyzer, polyethylene-based resin and solvent are purified and are all carried out under inert gas atmosphere.The solvent used in the manufacture of the modulation of modification hectorite, the modulation of catalyzer, polyethylene-based resin etc. all use by previous known method purified, the material of dry, deoxidation.Two (cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases, propane-1, two (cyclopentadienyl) zirconium dichlorides of 3-bis-bases, phenylbenzene methylene radical (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, dimethylsilane two bases (cyclopentadienyl) (4,7-dimethyl indenyl) zirconium dichloride, 1,1,3,3-tetramethyl disiloxane-1, two (cyclopentadienyl) zirconium dichlorides of 3-bis-bases, phenylbenzene methylene radical (1-indenyl) (9-fluorenyl) zirconium dichloride are used material synthetic by known method, that identify.The hexane solution of triisobutyl aluminium (0.714M) is used Tosoh FinechemCorporation to manufacture.
synthesis example 1
[modulation of modification hectorite]
Add 100 milliliters of 3 liters of ethanol and 37% concentrated hydrochloric acids in 3 premium on currency after, in gained solution, add N, N-dimethyl-stearylamine 330g (1.1mol), be heated to 60 ℃, thus modulation hydrochloride solution.Add hectorite 1kg in this solution.By this suspension under 60 ℃, stir 3 hours, after removing supernatant liquor, with the water 50L of 60 ℃ washing.Thereafter, at 60 ℃, 10
-3under torr dry 24 hours, pulverize by airflow milling, thereby obtain the modification hectorite of median size 5.2 μ m.
[modulation of catalyzer (p)]
Aforementioned modification hectorite 500g is suspended in 1.7 liters of hexanes, add the mixed solution of the hexane solution (0.714M) 2.8 liters (2mol) of dimethylsilane two bases (cyclopentadienyl) (2-methyl indenyl) zirconium dichloride 8.25g (20.0mmol) and triisobutyl aluminium, under 60 ℃, stir after 3 hours, the standing supernatant liquor of removing, and then the hexane solution (0.15M) of interpolation triisobutyl aluminium, make catalyst precursor slurry (100g/L).
In the catalyst precursor slurry of above-mentioned modulation, add the isopropylidene (1-cyclopentadienyl) (2 of 10mol% with respect to dimethylsilane two bases (cyclopentadienyl) (2-methyl indenyl) zirconium dichloride, 7-di-t-butyl-9-fluorenyl) zirconium dichloride 1.21g (2.22mmol), at room temperature stir 6 hours.The standing supernatant liquor of removing, and then add the hexane solution (0.15M) of triisobutyl aluminium, finally obtain the catalyst pulp of 100g/L.
[manufacture of polyethylene-based resin (B-1)]
Import 5.9 liters of 300 liters of hexanes and 1-butylene in the polymerizer of 540 liters of internal volumes, the interior temperature of autoclave is warming up to 70 ℃.Add aforementioned catalyzer (p) 120 milliliters in this autoclave, import ethene/hydrogen gas mixture (hydrogen 500ppm) until dividing potential drop is 0.9MPa, start polymerization.In polymerization, import continuously ethene/hydrogen gas mixture (hydrogen 500ppm) so that dividing potential drop is remained to 0.9MPa.In addition, polymerization temperature control is 70 ℃.After polymerization starts after 90 minutes the interior pressure-off of aggregation container is pressed, filtering content thing, drying, obtain 54kg polyethylene-based resin powder.The density of gained polyethylene-based resin (B-1) is 924kg/m
3, MFR is that 25g/10 minute, long-chain side chain number are that every 1000 carbon atoms are 0.13, MS
190for 22mN, MS
160for 34mN.
In addition, in this Production Example, carry out the manufacture of the macromonomer shown in following reference example 1 and carry out the manufacture of polyethylene-based resin (B-1) by ethene and 1-butylene copolymerization under the coexisting of this macromonomer.
Reference example 1
[manufacture of macromonomer]
Replace catalyzer (p) and add the modulation of synthesis example 1[catalyzer (p)] in 120 milliliters, the catalyst precursor slurry of modulation, in addition, with the manufacture with synthesis example 1[polyethylene-based resin (B-1)] same method carries out polymerization, obtains ethylene copolymer powders.The M of gained ethylene copolymer
n=15500, M
w/ M
n=2.25, Z=0.28.In addition, do not detect the long-chain side chain.
synthesis example 2
[manufacture of polyethylene-based resin (B-2)]
Import 5.6 liters of 1-butylene, add the modulation of synthesis example 1[catalyzer (p)] in 131 milliliters of the catalyzer (p) of modulation, replace ethene/hydrogen gas mixture and only use ethene, in addition, with the manufacture with synthesis example 1[polyethylene-based resin (B-1)] same method carries out polymerization, obtains the polyethylene-based resin powder of 57kg.The density of gained polyethylene-based resin (B-2) is 924kg/m
3, MFR is that 15g/10 minute, every 1000 carbon atoms of long-chain side chain number are 0.13, MS
190for 24mN, MS
160for 38mN.
In addition, in this Production Example, carry out the manufacture of the macromonomer shown in following reference example 2 and carry out the manufacture of polyethylene-based resin (B-1) by ethene and 1-butylene copolymerization under the coexisting of this macromonomer.
reference example 2
[manufacture of macromonomer]
Replace catalyzer (p) and add the modulation of synthesis example 1[catalyzer (p)] in 131 milliliters, the catalyst precursor slurry of modulation, in addition, with the manufacture with synthesis example 2[polyethylene-based resin (B-2)] same method carries out polymerization, obtains ethylene copolymer powders.The M of gained ethylene copolymer
n=16000, M
w/ M
n=2.35, Z=0.28.In addition, do not detect the long-chain side chain.
synthesis example 3
[modulation of catalyzer (q)]
Replace dimethylsilane two bases (cyclopentadienyl) (2-methyl indenyl) zirconium dichloride and add dimethylsilane two bases (cyclopentadienyl) (4,7-dimethyl indenyl) zirconium dichloride 8.53g (20.0mmol), replace isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and add phenylbenzene methylene radical (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride 0.70g (1.05mmol), in addition, with the modulation with synthesis example 1[catalyzer (p)] same method modulated, and obtains the catalyst pulp of 100g/L.
[manufacture of polyethylene-based resin (B-3)]
Import 5.2 liters of 1-butylene, replace catalyzer (p) and add 106 milliliters of aforementioned catalyzer (q), replace ethene/hydrogen gas mixture and use ethene, in addition, with the manufacture with synthesis example 1[polyethylene-based resin (B-1)] same method carries out polymerization, obtains the polyethylene-based resin powder of 55kg.The density of gained polyethylene-based resin (B-3) is 924kg/m
3, MFR is that 5g/10 minute, every 1000 carbon atoms of long-chain side chain number are 0.10, MS
190for 44mN, MS
160for 66mN.
In addition, in this Production Example, carry out the manufacture of the macromonomer shown in following reference example 3 and carry out the manufacture of polyethylene-based resin (B-3) by ethene and 1-butylene copolymerization under the coexisting of this macromonomer.
reference example 3
[manufacture of macromonomer]
Replace catalyzer (q) and add the modulation of synthesis example 3[catalyzer (q)] in 106 milliliters, the catalyst precursor slurry of modulation, in addition, with the manufacture with synthesis example 3[polyethylene-based resin (B-3)] same method carries out polymerization, obtains ethylene copolymer powders.The M of gained ethylene copolymer
n=19000, M
w/ M
n=2.50, Z=0.25.In addition, do not detect the long-chain side chain.
synthesis example 4
[modulation of catalyzer (r)]
Replace dimethylsilane two bases (cyclopentadienyl) (2-methyl indenyl) zirconium dichloride and add dimethylsilane two bases (cyclopentadienyl) (2-methyl indenyl) zirconium dichloride 7.43g (18.0mmol) and 1,1,3,3-tetramethyl disiloxane-1, two (cyclopentadienyl) zirconium dichloride 0.85g (2.0mmol) of 3-bis-bases, in addition, with the modulation with synthesis example 1[catalyzer (p)] same method modulated, and obtains the catalyst pulp of 100g/L.
[manufacture of polyethylene-based resin (B-4)]
Import 6.4 liters of 1-butylene, replace catalyzer (p) and add 133 milliliters of aforementioned catalyzer (r), replace ethene/hydrogen gas mixture (hydrogen 500ppm) and use ethene/hydrogen gas mixture (hydrogen 1000ppm), in addition, with the manufacture with synthesis example 1[polyethylene-based resin] same method carries out polymerization, obtains the polyethylene-based resin powder of 53kg.The density of gained polyethylene-based resin (B-4) is 924kg/m
3, MFR is that 15g/10 minute, every 1000 carbon atoms of long-chain side chain number are 0.12, MS
190for 27mN, MS
160for 40mN.
In addition, in this Production Example, carry out the manufacture of the macromonomer shown in following reference example 4 and carry out the manufacture of polyethylene-based resin (B-4) by ethene and 1-butylene copolymerization under the coexisting of this macromonomer.
reference example 4
[manufacture of macromonomer]
Replace catalyzer (r) and add the modulation of synthesis example 4[catalyzer (r)] in 133 milliliters, the catalyst precursor slurry of modulation, in addition, with the manufacture with synthesis example 4[polyethylene-based resin (B-4)] same method carries out polymerization, obtains ethylene copolymer powders.The M of gained ethylene copolymer
n=16000, M
w/ M
n=2.75, Z=0.27.In addition, do not detect the long-chain side chain.
synthesis example 5
[modulation of catalyzer (s)]
Replace dimethylsilane two bases (cyclopentadienyl) (2-methyl indenyl) zirconium dichloride and add dimethylsilane two bases (cyclopentadienyl) (4,7-dimethyl indenyl) zirconium dichloride 6.83g (16.0mmol), replace isopropylidene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and add phenylbenzene methylene radical (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride 2.68g (4.0mmol), in addition, with the modulation with synthesis example 1[catalyzer (p)] same method modulated, and obtains the catalyst pulp of 100g/L.
[manufacture of polyethylene-based resin (B-5)]
Import 7.6 liters of 1-butylene, replace catalyzer (p) and add 135 milliliters of aforementioned catalyzer (s), replace ethene/hydrogen gas mixture and use ethene, polymerization temperature is controlled to 60 ℃, in addition, with the manufacture with synthesis example 1[polyethylene-based resin (B-1)] same method carries out polymerization, obtains the polyethylene-based resin powder of 54kg.The density of gained polyethylene-based resin (B-5) is 918kg/m
3, MFR is that 5g/10 minute, every 1000 carbon atoms of long-chain side chain number are 0.10, MS
190for 49mN, MS
160for 70mN.
In addition, in this Production Example, carry out the manufacture of the macromonomer shown in following reference example 5 and carry out the manufacture of polyethylene-based resin (B-5) by ethene and 1-butylene copolymerization under the coexisting of this macromonomer.
reference example 5
[manufacture of macromonomer]
Replace catalyzer (s) and add the modulation of synthesis example 5[catalyzer (s)] in 135 milliliters, the catalyst precursor slurry of modulation, in addition, with the manufacture with synthesis example 5[polyethylene-based resin (B-5)] same method carries out polymerization, obtains ethylene copolymer powders.The M of gained ethylene copolymer
n=21000, M
w/ M
n=2.48, Z=0.25.In addition, do not detect the long-chain side chain.
synthesis example 6
[modulation of catalyzer (t)]
Modulation by synthesis example 1[modification hectorite] in the modification hectorite 500g of modulation be suspended in 1.8 liters of hexanes, 2.9 liters of the hexane solutions (0.714M) of interpolation triisobutyl aluminium, under room temperature, stirring is 1 hour, thereby obtains the product of contact of modification hectorite and triisobutyl aluminium.On the other hand, add two (cyclopentadienyl) zirconium dichloride 6.97g (20mmol) of dimethylsilane two bases are dissolved in to the material that toluene obtains, stir an evening under room temperature, thereby obtain catalyst pulp (100g/L).
[manufacture of macromonomer]
Import 7.6 liters of 1-butylene, replace catalyzer (p) and add 135 milliliters of aforementioned catalyzer (t), replace ethene/hydrogen gas mixture and use ethene, ethylene partial pressure is controlled to 1.2MPa, polymerization temperature is controlled at 85 ℃, in addition, use the manufacture with synthesis example 1[polyethylene-based resin (B-1)] same method carries out polymerization.The M of the macromonomer of deviating from from this polymerizer
n=10950, M
w/ M
n=2.61, Z=0.57.In addition, do not detect the long-chain side chain.
[manufacture of polyethylene-based resin (B-6)]
In the polymerizer of 540 liters of the internal volumes of the macromonomer that contains above-mentioned manufacture, import 0.75 liter of hexane solution (0.714mol/L) and phenylbenzene methylene radical (1-indenyl) (9-fluorenyl) the zirconium dichloride 3.75mmol of 0.22 liter of 1-butylene and triisobutyl aluminium, the interior temperature of autoclave is warming up to 85 ℃.It is 0.2MPa that importing ethene/hydrogen gas mixture (hydrogen 22000ppm) makes dividing potential drop, starts polymerization.In polymerization, import continuously ethene/hydrogen gas mixture and make dividing potential drop remain 0.2MPa.In addition, polymerization temperature is controlled at 85 ℃.After polymerization starts 90 minutes, after the interior pressure-off of autoclave is pressed, the suction filtration content.After drying, obtain the polyethylene-based resin of 54kg.The density of gained polyethylene-based resin (B-6) is 948kg/m
3, MFR is that 30g/10 minute, every 1000 carbon atoms of long-chain side chain number are 0.15, MS
190for 21mN, MS
160for 30mN.
synthesis example 7
[manufacture of polyethylene-based resin (B-7)]
Do not add 1-butylene, in addition, use the manufacture with synthesis example 6[polyethylene-based resin (B-6)] same method carries out polymerization, obtains the polyethylene-based resin of 50kg.The density of gained polyethylene-based resin (B-7) is 963kg/m
3, MFR is that 15g/10 minute, every 1000 carbon atoms of long-chain side chain number are 0.12, MS
190for 30mN, MS
160for 55mN.
The characteristic of the characteristic of the macromonomer in synthesis example 1～7 and polyethylene-based resin (B-1)～(B-7) is shown in table 1.
The characteristic of the Low Density Polyethylene used in following embodiment and comparative example is shown in table 2.
[table 2]
embodiment 1
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) (below, be called (A-1).) after polyethylene-based resin (B-3) 85 % by weight shown in 15 % by weight, synthesis example 3, be adjusted to the single screw extrusion machine (PLACOCO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 2
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd manufactures; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) after polyethylene-based resin (B-2) 95 % by weight shown in (A-2) 5 % by weight, synthesis example 2, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 3
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-2) 50 % by weight shown in (A-1) 50 % by weight, synthesis example 2, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 4
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd manufactures; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) after polyethylene-based resin (B-1) 85 % by weight shown in (A-2) 15 % by weight, synthesis example 1, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 5
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-4) 75 % by weight shown in (A-1) 25 % by weight, synthesis example 4, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 6
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-5) 90 % by weight shown in (A-1) 10 % by weight, synthesis example 5, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 7
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-6) 97.5 % by weight shown in (A-1) 2.5 % by weight, synthesis example 6, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 8
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd manufactures; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) after polyethylene-based resin (B-7) 92.5 % by weight shown in (A-2) 7.5 % by weight, synthesis example 7, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 9
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene217 that TOSOH Co., Ltd manufactures; Density 923kg/m
3, MFR4.5g/10 minute, MS
160160mN) after polyethylene-based resin (B-4) 75 % by weight shown in (A-3) 25 % by weight, synthesis example 4, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
embodiment 10
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene3MO4A that TOSOH Co., Ltd manufactures; Density 924.5kg/m
3, MFR4.5g/10 minute, MS
160110mN) after polyethylene-based resin (B-4) 75 % by weight shown in (A-4) 25 % by weight, synthesis example 4, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 3.
comparative example 1
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-3) 99.5 % by weight shown in (A-1) 0.5 % by weight, synthesis example 3, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4.
When the gained polyethylene resin composition is extruded to lamination, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) is compared to curve inwardly and is become large, for bad.
comparative example 2
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-3) 45 % by weight shown in (A-1) 55 % by weight, synthesis example 3, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Survey property density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4.
When the gained polyethylene resin composition is extruded to lamination, comparing can't be by the minimum film thickness attenuation, for bad for the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures).
comparative example 3
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd manufactures; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) after polyethylene-based resin (B-2) 99.5 % by weight shown in (A-2) 0.5 % by weight, synthesis example 2, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4.
When the gained polyethylene resin composition is extruded to lamination, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) is compared to curve inwardly and is become large, for bad.
comparative example 4
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) after polyethylene-based resin (B-2) 45 % by weight shown in (A-1) 55 % by weight, synthesis example 2, be adjusted to single screw extrusion machine (the PLACO CO. of 180 ℃ at barrel zone temperature, LTD. manufacture, pattern PDA-50) in melting mixing, granulation, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4.
When the gained polyethylene resin composition is extruded to lamination, the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) is compared and can't be made the minimum film thickness attenuation, for bad.
comparative example 5
The Low Density Polyethylene obtained by the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd manufactures; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) (A-2) 15 % by weight, straight chain shape Low Density Polyethylene (the trade(brand)name Nipolon Z 04P66A that TOSOH Co., Ltd manufactures that obtained by the metallocene series catalysts; Density 917kg/m
3, MFR15g/10 minute) (C-1) after 85 % by weight, be adjusted to melting mixing, granulation in the single screw extrusion machine (PLACO CO., LTD. manufactures, pattern PDA-50) of 180 ℃ at barrel zone temperature, obtain the particle of polyethylene resin composition.The gained particle is by the method laminating molding shown in the evaluation method of polyethylene-based resin.
Measure density, MFR, MS by the gained polyethylene resin composition, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4.
When the gained polyethylene resin composition is extruded to lamination, only obtain identical the curving inwardly of high-pressure process Low Density Polyethylene (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) be shaped with the same terms laminated, the appearance poor of fused films.
comparative example 6
According to the method shown in the evaluation method of polyethylene-based resin, to Low Density Polyethylene (the trade(brand)name Petrothene205 that TOSOH Co., Ltd manufactures obtained by the high-pressure free radical polymerization; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) (A-2) 100 % by weight are carried out laminating molding.
Measure MS, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4, only obtain the high-pressure process Low Density Polyethylene (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) that is shaped with the same terms laminated identical curve inwardly, the outward appearance of fused films, the pollution on cooling roller surface, minimum film thickness is thicker, for bad.
comparative example 7
According to the method shown in the evaluation method of polyethylene-based resin, polyethylene-based resin (B-4) 100 % by weight shown in synthesis example 4 are carried out to laminating molding.
Measure MS, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4, and the high-pressure process Low Density Polyethylene be shaped with the same terms laminated (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) is compared and curved inwardly greatly, for bad.
comparative example 8
According to the method shown in the evaluation method of polyethylene-based resin, to straight chain shape Low Density Polyethylene (the trade(brand)name Nipolon-Z 04P 66A that TOSOH Co., Ltd manufactures obtained by the metallocene series catalysts; Density 917kg/m
3, MFR15g/10 divides) (C-1) 100 % by weight carry out laminating molding.
Measure MS, attempt the extruding layer pressing formation, because fused film is unstable, can't obtain layered product.In addition, the evaluation result of the pollution on the outward appearance of fused films, cooling roller surface is shown in table 4, only obtains the performance identical with the high-pressure process Low Density Polyethylene of estimating under the same terms (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures).
comparative example 9
According to the method shown in the evaluation method of polyethylene-based resin, to Low Density Polyethylene (the trade(brand)name Petrothene360 that TOSOH Co., Ltd manufactures obtained by the high-pressure free radical polymerization; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) (A-1) 100 % by weight are carried out laminating molding.
Measure MS, attempt the extruding layer pressing formation, can't improve the inbound pacing of base material, can't obtain layered product.In addition, the evaluation result of the pollution on the outward appearance of fused films, cooling roller surface is shown in table 4, only obtains the performance identical with the high-pressure process Low Density Polyethylene of estimating under the same terms (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures).
comparative example 10
According to the method shown in the evaluation method of polyethylene-based resin, to Low Density Polyethylene (the trade(brand)name Petrothene217 that TOSOH Co., Ltd manufactures obtained by the high-pressure free radical polymerization; Density 923kg/m
3, MFR4.5g/10 minute, MS
160160mN) (A-3) 100 % by weight are carried out laminating molding.
Measure MS, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4, only obtain the high-pressure process Low Density Polyethylene (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) that is shaped with the same terms laminated identical curve inwardly, the outward appearance of fused films, the pollution on cooling roller surface, minimum film thickness is thicker, for bad.
comparative example 11
According to the method shown in the evaluation method of polyethylene-based resin, to Low Density Polyethylene (the trade(brand)name Petrothene3M04A that TOSOH Co., Ltd manufactures obtained by the high-pressure free radical polymerization; Density 924.5kg/m
3, MFR4.5g/10 minute, MS
160110mN) (A-4) 100 % by weight are carried out laminating molding.
Measure MS, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4, only obtain the outward appearance of the fused films identical with the high-pressure process Low Density Polyethylene (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures) of the same terms laminated shaping, the pollution on cooling roller surface, curve inwardly large, minimum film thickness is also thicker, for bad.
comparative example 12
According to the method shown in the evaluation method of polyethylene-based resin, to Low Density Polyethylene (the trade(brand)name Petrothene203 that TOSOH Co., Ltd manufactures obtained by the high-pressure free radical polymerization; Density 919kg/m
3, MFR8g/10 minute, MS
16070mN) (A-5) 100 % by weight are carried out laminating molding.
Measure MS, when the extruding layer pressing formation, estimate curve inwardly, minimum film thickness, the outward appearance of fused films, the pollution on cooling roller surface.These evaluation results are shown in table 4.
Claims (5)
1. a polyethylene resin composition, is characterized in that, it comprises: the density obtained by the high-pressure free radical polymerization is 915～935kg/m
3, the melt mass flow rate MFR that measures under 190 ℃ of 2.16kg loads is 0.5～5.0g/10 minute, at the melting tension force MS of 160 ℃ of mensuration
160for the Low Density Polyethylene more than 150mN (A) 1～50 % by weight; And polyethylene-based resin (B) 99～50 % by weight that meet the condition of following (a)～(c),
(a) density is 910～965kg/m
3,
(b) the long-chain side chain number of carbon number more than 6 be 0.01～3.0 of every 1000 carbon atom,
(c) the melting tension force MS that is mN in the unit of 190 ℃ of mensuration
190the MFR that is g/10 minute with the unit measured under 190 ℃ of 2.16kg loads meets following formula (1)
MS
190＞22×MFR
-0.88（1）
And the melting tension force MS that is mN in the unit of 160 ℃ of mensuration
160the MFR that is g/10 minute with the unit measured under 190 ℃ of 2.16kg loads meets following formula (2)
MS
160＞110-110×log（MFR）（2）。
2. polyethylene resin composition according to claim 1, it is characterized in that, under the existence of macromonomer, or in synthetic this macromonomer, using ethene and the arbitrarily olefinic polymerization of carbon number more than the 3 and polyethylene-based resin that obtains is used as polyethylene-based resin (B)
Described macromonomer has by the end obtained by polymerising ethylene the ethylene copolymer that the ethene polymers of vinyl or the olefin-copolymerization more than 3 obtains by ethene and carbon number end have a vinyl and forms, and, described macromonomer
(d) number-average molecular weight M
nbe more than 2000,
(e) weight-average molecular weight M
wwith number-average molecular weight M
nratio M
w/ M
nbe 2.0～5.0.
3. polyethylene resin composition according to claim 1 and 2, is characterized in that, meets the condition of following (f)～(h):
(f) density is 915～965kg/m
3,
(g) MFR measured under 190 ℃ of 2.16kg loads be 3.0～30.0g/10 minute,
(h) at the melting tension force MS of 160 ℃ of mensuration
160more than 30mN.
4. according to claim 1 or 2 described polyethylene resin compositions, it is characterized in that, for extruding lamination.
5. a layered product, is characterized in that, it has at least above layer formed by claim 1 or 2 described polyethylene resin compositions of one deck.
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| JP5707848B2 (en) * | 2010-10-21 | 2015-04-30 | 東ソー株式会社 | Foamed laminate for microwave cooking |
| JP2012136665A (en) * | 2010-12-27 | 2012-07-19 | Tosoh Corp | Ethylenic polymer composition for extrusion lamination, and laminated body |
| JP2012136666A (en) * | 2010-12-27 | 2012-07-19 | Tosoh Corp | Polyethylene resin composition for extrusion laminate and laminated body |
| JP5747501B2 (en) * | 2010-12-27 | 2015-07-15 | 東ソー株式会社 | LAMINATE, RELEASE SHEET COMPRISING THE SAME, AND SUBSTRATE FOR ADHESIVE TAPE |
| JP5825023B2 (en) * | 2011-09-30 | 2015-12-02 | 東ソー株式会社 | Laminated body |
| JP5895447B2 (en) * | 2011-10-25 | 2016-03-30 | 東ソー株式会社 | Polyethylene resin composition for extrusion lamination and laminate |
| JP5895483B2 (en) * | 2011-11-30 | 2016-03-30 | 東ソー株式会社 | Ethylene polymer composition for extrusion lamination and laminate |
| JP5895484B2 (en) * | 2011-11-30 | 2016-03-30 | 東ソー株式会社 | Ethylene polymer composition for extrusion lamination and laminate |
| JP5810880B2 (en) * | 2011-12-13 | 2015-11-11 | 東ソー株式会社 | Ethylene polymer and process for producing the same |
| WO2017139096A1 (en) * | 2016-02-12 | 2017-08-17 | Dow Global Technologies Llc | Cast films, and articles made therefrom |
| JP6159494B1 (en) * | 2017-01-27 | 2017-07-05 | 加川 清二 | Easy tear plastic film and manufacturing apparatus thereof |
| JP7279300B2 (en) * | 2017-03-28 | 2023-05-23 | 東ソー株式会社 | Resin composition and film made of the same |
| WO2019117209A1 (en) * | 2017-12-12 | 2019-06-20 | 日本ポリエチレン株式会社 | Polyethylene resin composition for use in lamination, laminate, and production method for laminate |
| JP6450486B1 (en) * | 2018-04-13 | 2019-01-09 | 株式会社旭パック | Polyethylene sheet, composite sheet and method for producing polyethylene sheet |
| US11367588B2 (en) | 2018-07-25 | 2022-06-21 | Hitachi High-Tech Corporation | Charged particle beam device |
| JP7310445B2 (en) * | 2018-09-12 | 2023-07-19 | 東ソー株式会社 | Polyethylene resin composition, laminate and medical container |
| KR102358766B1 (en) * | 2020-05-22 | 2022-02-04 | 한화토탈 주식회사 | Polyethylene resin composition and separator for secondary battery produced therefrom |
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| JP4670327B2 (en) * | 2004-11-26 | 2011-04-13 | 東ソー株式会社 | Heat resistant film |
| JP4923423B2 (en) * | 2005-03-24 | 2012-04-25 | 東ソー株式会社 | Ethylene resin composition for extrusion lamination |
| JP4641842B2 (en) * | 2005-03-25 | 2011-03-02 | 旭化成ケミカルズ株式会社 | Polyethylene resin composition for extrusion lamination |
| JP2006299167A (en) * | 2005-04-22 | 2006-11-02 | Tosoh Corp | Inflation film |
| JP2006306408A (en) * | 2005-04-26 | 2006-11-09 | Tosoh Corp | Multilayer container |
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| JP2009293014A (en) | 2009-12-17 |
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| CN101575430A (en) | 2009-11-11 |
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