CN101575430A - Polyethylene resin composition and laminating body formed therefrom - Google Patents
Polyethylene resin composition and laminating body formed therefrom Download PDFInfo
- Publication number
- CN101575430A CN101575430A CNA2009101376764A CN200910137676A CN101575430A CN 101575430 A CN101575430 A CN 101575430A CN A2009101376764 A CNA2009101376764 A CN A2009101376764A CN 200910137676 A CN200910137676 A CN 200910137676A CN 101575430 A CN101575430 A CN 101575430A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- mfr
- based resin
- resin composition
- cyclopentadienyl
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 71
- 229920013716 polyethylene resin Polymers 0.000 title claims abstract description 67
- 238000010030 laminating Methods 0.000 title abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000003475 lamination Methods 0.000 claims abstract description 30
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 25
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 8
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 8
- 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 51
- 238000006116 polymerization reaction Methods 0.000 claims description 39
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 21
- 229920001038 ethylene copolymer Polymers 0.000 claims description 18
- 230000004927 fusion Effects 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 20
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract 2
- -1 polyethylenes Polymers 0.000 description 215
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 100
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 57
- 235000010290 biphenyl Nutrition 0.000 description 56
- 239000000203 mixture Substances 0.000 description 55
- 238000000465 moulding Methods 0.000 description 55
- 238000004519 manufacturing process Methods 0.000 description 52
- 230000015572 biosynthetic process Effects 0.000 description 45
- 238000003786 synthesis reaction Methods 0.000 description 45
- 238000011156 evaluation Methods 0.000 description 44
- 239000000047 product Substances 0.000 description 37
- 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
- 230000008569 process Effects 0.000 description 23
- 239000000463 material Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 21
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 238000002844 melting Methods 0.000 description 17
- 230000008018 melting Effects 0.000 description 17
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 16
- 238000005469 granulation Methods 0.000 description 15
- 230000003179 granulation Effects 0.000 description 15
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 14
- 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
- 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
- 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
- 239000002002 slurry Substances 0.000 description 9
- 239000000243 solution Substances 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
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 8
- 238000012986 modification Methods 0.000 description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 239000012018 catalyst precursor Substances 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
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002655 kraft paper Substances 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 229910000077 silane Inorganic materials 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
- 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-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
- 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
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 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
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 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
- 238000003756 stirring Methods 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
- 229910052726 zirconium Inorganic materials 0.000 description 3
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 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
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-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
- 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
- 238000005481 NMR spectroscopy Methods 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
- 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
- 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
- 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
- 239000002734 clay mineral Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 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
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 2
- FFUUQWKRQSBSGU-UHFFFAOYSA-N dipropylsilicon Chemical compound CCC[Si]CCC FFUUQWKRQSBSGU-UHFFFAOYSA-N 0.000 description 2
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 125000005574 norbornylene group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000015067 sauces Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DNZJAVZFZWYHSW-UHFFFAOYSA-L C(C(C1=CC=CC=C11)[Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C1C1=CC=CC=C1.[Cl-].[Cl-] Chemical compound C(C(C1=CC=CC=C11)[Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C1C1=CC=CC=C1.[Cl-].[Cl-] DNZJAVZFZWYHSW-UHFFFAOYSA-L 0.000 description 1
- GHUKOKVWXDIIFZ-UHFFFAOYSA-L C(C=C1)C([Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C1C1=CC=CC=C1.[Cl-].[Cl-] Chemical compound C(C=C1)C([Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C1C1=CC=CC=C1.[Cl-].[Cl-] GHUKOKVWXDIIFZ-UHFFFAOYSA-L 0.000 description 1
- BLYGPSAIGZRMHZ-UHFFFAOYSA-L CC(C)(C)C(C=C1)=CC2=C1C1=CC=C(C(C)(C)C)C=C1C2[Zr+2]C1=CC(C2=CC=CC=C2)=CC1.[Cl-].[Cl-] Chemical compound CC(C)(C)C(C=C1)=CC2=C1C1=CC=C(C(C)(C)C)C=C1C2[Zr+2]C1=CC(C2=CC=CC=C2)=CC1.[Cl-].[Cl-] BLYGPSAIGZRMHZ-UHFFFAOYSA-L 0.000 description 1
- QVZJKDFSDLKFFM-UHFFFAOYSA-L CC(C1)=C(C)C=C1[Zr+2]C1C(C=C(C)C=C2)=C2C2=CC=C(C)C=C12.[Cl-].[Cl-] Chemical compound CC(C1)=C(C)C=C1[Zr+2]C1C(C=C(C)C=C2)=C2C2=CC=C(C)C=C12.[Cl-].[Cl-] QVZJKDFSDLKFFM-UHFFFAOYSA-L 0.000 description 1
- ZIYSDNOZWRDVJF-UHFFFAOYSA-L CC(C1)=CC(C)=C1[Zr+2]C1C2=CC=CC=C2C2=C1C=CC=C2.[Cl-].[Cl-] Chemical compound CC(C1)=CC(C)=C1[Zr+2]C1C2=CC=CC=C2C2=C1C=CC=C2.[Cl-].[Cl-] ZIYSDNOZWRDVJF-UHFFFAOYSA-L 0.000 description 1
- COLFJMUAPJTPOA-UHFFFAOYSA-L CC(C=C1)=CC2=C1C1=CC=C(C)C=C1C2[Zr+2]C1C2=CC=CC=C2C=C1.[Cl-].[Cl-] Chemical compound CC(C=C1)=CC2=C1C1=CC=C(C)C=C1C2[Zr+2]C1C2=CC=CC=C2C=C1.[Cl-].[Cl-] COLFJMUAPJTPOA-UHFFFAOYSA-L 0.000 description 1
- FKDQFOVJSDCTAZ-UHFFFAOYSA-L CC1C([Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C(C)C(C)=C1C.[Cl-].[Cl-] Chemical compound CC1C([Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C(C)C(C)=C1C.[Cl-].[Cl-] FKDQFOVJSDCTAZ-UHFFFAOYSA-L 0.000 description 1
- XXAHSGLVXTVYAW-UHFFFAOYSA-L CC1C([Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C(C)C=C1.[Cl-].[Cl-] Chemical compound CC1C([Zr+2]C2C3=CC=CC=C3C3=C2C=CC=C3)=C(C)C=C1.[Cl-].[Cl-] XXAHSGLVXTVYAW-UHFFFAOYSA-L 0.000 description 1
- STSPYWZUSSGQJZ-UHFFFAOYSA-L CCC(C=C1C2[Zr+2])=CC=C1C1=C2C(C2C=CC=C2)=C(CC)C=C1.[Cl-].[Cl-] Chemical compound CCC(C=C1C2[Zr+2])=CC=C1C1=C2C(C2C=CC=C2)=C(CC)C=C1.[Cl-].[Cl-] STSPYWZUSSGQJZ-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- UKUKRHDGWGRCFZ-UHFFFAOYSA-L [Cl-].[Cl-].C(C)C=1C=C(CC=1)[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=CC1=2)C)C Chemical compound [Cl-].[Cl-].C(C)C=1C=C(CC=1)[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=CC1=2)C)C UKUKRHDGWGRCFZ-UHFFFAOYSA-L 0.000 description 1
- OWACANPRMINNGI-UHFFFAOYSA-L [Cl-].[Cl-].C1(=CC=CC=C1)C=1C=C(CC1)[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=CC12)C)C Chemical compound [Cl-].[Cl-].C1(=CC=CC=C1)C=1C=C(CC1)[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=CC12)C)C OWACANPRMINNGI-UHFFFAOYSA-L 0.000 description 1
- UTZALKBJGHFTPM-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC2=CC=CC=C12)[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=CC1=2)C(C)(C)C)C(C)(C)C Chemical compound [Cl-].[Cl-].C1(C=CC2=CC=CC=C12)[Zr+2]C1C2=CC(=CC=C2C=2C=CC(=CC1=2)C(C)(C)C)C(C)(C)C UTZALKBJGHFTPM-UHFFFAOYSA-L 0.000 description 1
- UFRFWNKLPNLIJN-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)C1=C(C=CC=2C3=CC=C(C=C3C(C1=2)[Zr+2])C)C Chemical compound [Cl-].[Cl-].C1(C=CC=C1)C1=C(C=CC=2C3=CC=C(C=C3C(C1=2)[Zr+2])C)C UFRFWNKLPNLIJN-UHFFFAOYSA-L 0.000 description 1
- QDJZMNJUQNCKAX-UHFFFAOYSA-L [Cl-].[Cl-].C1C=C(C=C1[Zr++]C1c2ccccc2-c2ccccc12)c1ccccc1 Chemical compound [Cl-].[Cl-].C1C=C(C=C1[Zr++]C1c2ccccc2-c2ccccc12)c1ccccc1 QDJZMNJUQNCKAX-UHFFFAOYSA-L 0.000 description 1
- BOVBAKJVXIRQAK-UHFFFAOYSA-L [Cl-].[Cl-].CC(C)(C)c1ccc-2c(c1)C([Zr++])c1cc(ccc-21)C(C)(C)C Chemical compound [Cl-].[Cl-].CC(C)(C)c1ccc-2c(c1)C([Zr++])c1cc(ccc-21)C(C)(C)C BOVBAKJVXIRQAK-UHFFFAOYSA-L 0.000 description 1
- IBAQTLQYJRSPEC-UHFFFAOYSA-L [Cl-].[Cl-].CC1=C(C)C=C(C1)[Zr++]C1c2ccccc2-c2ccccc12 Chemical compound [Cl-].[Cl-].CC1=C(C)C=C(C1)[Zr++]C1c2ccccc2-c2ccccc12 IBAQTLQYJRSPEC-UHFFFAOYSA-L 0.000 description 1
- BXXBGNQNLNOSGU-UHFFFAOYSA-L [Cl-].[Cl-].CCC1=CCC([Zr++]C2c3ccccc3-c3ccccc23)=C1 Chemical compound [Cl-].[Cl-].CCC1=CCC([Zr++]C2c3ccccc3-c3ccccc23)=C1 BXXBGNQNLNOSGU-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- PMSZNCMIJVNSPB-UHFFFAOYSA-N bis(ethenyl)silicon Chemical compound C=C[Si]C=C PMSZNCMIJVNSPB-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IQSBKDJPSOMMRZ-UHFFFAOYSA-N ethenyl(methyl)silane Chemical compound C[SiH2]C=C IQSBKDJPSOMMRZ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000009512 pharmaceutical packaging Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Graft Or Block Polymers (AREA)
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 (MS[190])(mN, 190 DEG C) and MFR (g/10 min) satisfies the formular (1): MS[190]> 22MFR<-0.88>, and the melt tension (MS[160]) (mN, 160 DEG C) and the MFR satisfies the formular (2): MS[160]> 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 present invention relates to polyethylene resin composition and by its layered product that forms.In more detail, relate to the good polyethylene resin composition of outward appearance excellence by extruding the product that lamination obtains and processibility and by its layered product that forms.
Background technology
By extruding in the middle of the layered product that lamination process obtains, one deck is that the layered product of polyethylene-based resin uses in extensive use fields such as kraft paper packing, soft packaging, developing out paper supporter, tape, various containers at least.In the past, as the polyethylene-based resin that uses in these layered products, the main chain new LDPE (film grade) (LDPE) that uses with excellent shaping processability.But the density of LDPE is generally 0.918～0.925g/cm
3, it is difficult changing rerum natura with variable density, for example thermotolerance, rigidity, gas barrier property etc., is restricted during use.In addition, the forming speed of LDPE is fast, and then laminate thickness is when thin, and fused films is split easily, and base material is easy to generate and engages badly under this condition, therefore, is difficult to obtain the product of stay in grade.On the other hand, straight chain shape new LDPE (film grade) (L-LDPE), straight chain shape high density polyethylene(HDPE) straight chain shaped polyethylenes such as (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 the method (for example with reference to patent documentation 1～4) that lamination process obtains layered product.But this method produces thermal degradation when and be easy to generate foul smell in layered product in the mixed processes of polyethylene-based resin, thereby produces the uneven layered product that can not get surface smoothing of fusion when making extrusion molding because of the mixing of polyethylene-based resin is bad in addition.
In addition, reported, in L-LDPE and HDPE, imported the long-chain side chain, need not to mix the technology (for example with reference to patent documentation 5) that LDPE just can improve shaping processability by changing the polymerizing catalyst of ethene.But, use the fusion tension force of the polyethylene-based resin that these technology obtain still not enough, be difficult to stably extrude laminating molding.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 objective of the invention is to, solve above-mentioned such prior art problems, provide the good polyethylene resin composition of outward appearance excellence by extruding the product that lamination obtains and processibility and by its layered product that forms.
The method that is used to deal with problems
The result that the present invention furthers investigate to achieve these goals finds.That is, the invention provides a kind of polyethylene resin composition, it is characterized in that it comprises: the density that obtains by the high-pressure free radical polymerization is 915～935kg/m
3, melt mass flow rate that 2.16kg load (190 ℃) is measured down (below, be called MFR.) be 0.5～5.0g/10 minute new LDPE (film grade) (A) 1～50 weight %; And polyethylene-based resin (B) 99～50 weight % that satisfy 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 per 1000 carbon atom,
(c) at the fusion tension force (MS of 190 ℃ of mensuration
190) (mN) and at the following MFR (g/10 minute) that measures of 2.16kg load (190 ℃) satisfy following formula (1)
MS
190＞22×MFR
-0.88(1)
And fusion tension force (MS 160 ℃ of mensuration
160) (mN) and at the following MFR (g/10 minute) that measures of 2.16kg load (190 ℃) satisfy following formula (2).
MS
160＞110-110×log(MFR)(2)
The effect of invention
Polyethylene resin composition of the present invention is good by the outward appearance excellence and the processibility of the product extruding lamination and obtain, and is useful with resin as extruding lamination.
Embodiment
Below, the present invention is described in detail.
Constitute of the present invention extrude lamination with polyethylene resin composition, by the new LDPE (film grade) (A) that the high-pressure free radical polymerization obtains, its density is 915～935kg/m
3Scope.The not enough 915kg/m of density
3The time, self tackiness of film increases, and might lump.On the other hand, density surpasses 935kg/m
3, the fusing point height of new LDPE (film grade) (A) then, low-temperature heat-sealing might worsen.
The MFR that the new LDPE (film grade) that uses among the present invention (A) is measured down at 2.16kg load (190 ℃) is 0.5～5.0g/10 minute scope, more preferably 0.7～3.0g/10 minute scope.MFR is in the time of not enough 0.5g/10 minute, and it is big that the load of the forcing machine when melt extruding becomes, and in addition, might worsen with the outward appearance of polyethylene resin composition for the layered product that obtains in extruding lamination process extruding lamination.On the other hand, MFR might become big above 5.0g/10 minute then curve inwardly (neck in).
The new LDPE (film grade) that uses among the present invention (A) is at the fusion tension force (MS of 160 ℃ of mensuration
160) be preferably more than the 100mN, more preferably more than the 150mN.Fusion tension force is 100mN when above, and the fused film during lamination process is stable, and processibility is good, and roller pollutes and reduce, and can obtain excellent spatter property.
The new LDPE (film grade) that uses among the present invention (A) can obtain by existing known high-pressure free radical polymerization, suitably selects in scope of the present invention.
Constituting the lamination of extruding of the present invention is 910kg/m with the density of the polyethylene-based resin (B) of polyethylene resin composition
3More than, 965kg/m
3Below.The not enough 910kg/m of density
3The time, the thermotolerance of gained layered product might non-constant.On the other hand, density surpasses 965kg/m
3The time, curling of layered product might become remarkable.
Weight-average molecular weight (the M that the straight chain shaped polyethylene of the polyethylene-based resin that uses among the present invention (B) converts
w) be preferred more than 10000, below 1000000.M
wLess than 10000 or surpass at 1000000 o'clock is difficult to extrude laminating molding, therefore, might can not get layered product.
MFR that measures down at 2.16kg load (190 ℃) of the polyethylene-based resin that uses among the present invention (B) be 0.1～100g/10 minute be preferred.Not enough 0.1g/10 minute or when surpassing 100g/10 minute, carry out extruding layer and be pressed into deformation and get significantly difficulty, therefore might can not get layered product.
The long-chain side chain number of the polyethylene-based resin that uses among the present invention (B) is that per 1000 carbon atoms are more than 0.01, below 3.0.During 0.01 of less than, carry out extruding layer and be pressed into deformation and get significantly difficulty, therefore, might can not get layered product.In addition, surpass 3.0 layered products that then might become the mechanical property difference of vinylite layer.In addition, long-chain side chain number be meant by
13C-NMR measures the number of the side chain of detected hexyl above (carbon number is more than 6).
The fusion tension force MS 190 ℃ of mensuration of the polyethylene-based resin that uses among the present invention (B)
190(mN) and the MFR (g/10 minute, 190 ℃) that measures down at 2.16kg load (190 ℃) be the relation shown in the following formula (1):
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)”
When not satisfying (1) formula, for example do not satisfy MS
190＞22 * MFR
-0.88L-LDPE and HDPE, carry out extruding layer and be pressed into deformation and get significantly difficulty, therefore, might can not get layered product.
In addition, the fusion tension force MS 160 ℃ of mensuration of the polyethylene-based resin that uses among the present invention (B)
160(mN) and at the following MFR (g/10 minute, 190 ℃) that measures of 2.16kg load (190 ℃) satisfy the relation shown in the following formula (2):
MS
160＞110-110×log(MFR)(2)
Be preferably and satisfy 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)”。
When not satisfying (2) formula, for example do not satisfy MS
160L-LDPE and the HDPE of＞110-110 * log (MFR) carry out extruding layer and are pressed into deformation and get significantly difficulty, therefore, might can not get layered product.
The polyethylene-based resin (B) that satisfies aforementioned condition (a) and (b), (c) that uses among the present invention, be preferably in the presence of macromonomer or with the synthetic of macromonomer simultaneously with vinyl polymerization resulting (being total to) polymkeric substance, wherein said macromonomer comprises the polymerisable polymkeric substance or the multipolymer of alkene.Promptly, it is following ethene (being total to) polymkeric substance, it is in the presence of following macromonomer, or with this macromonomer synthetic simultaneously, by independent polymerising ethylene, perhaps with ethene and carbon number more than 3 olefinic polymerization and obtain, this macromonomer is to have the olefin polymer of vinyl or the macromonomer that multipolymer forms by the end that olefin polymerization obtains, more preferably the end that obtains by independent polymerising ethylene has the ethene polymers of vinyl, perhaps, with ethene and carbon number more than 3 olefin-copolymerization and the 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 that uses as macromonomer have vinyl ethene polymkeric substance or terminally have multipolymer vinyl, ethene and the alkene of carbon number more than 3, be 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 in the presence of above-mentioned macromonomer, or with the synthetic of above-mentioned macromonomer simultaneously, use is with the catalyzer of the transistion metal compound shown in the following general formula (4) [composition (i)] as principal constituent, independent polymerising ethylene, perhaps the method for the olefin-copolymerization more than 3 is made with ethene and carbon number.
General formula (4):
M in the composition (i)
1Be 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 the composition (i)
1By following general formula (5), (6) or (7) expression, the substituent R in these formulas
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 the 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 the composition (i)
2By following general formula (8) expression, substituent R
5For example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.
General formula (8):
As the R shown in the 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
3With following general formula (9) expression, substituent R
6For example independent separately is the alkyl of hydrogen atom, halogen, carbon number 1～20.Y
1Be the atom of periodic table of elements IVA family, specifically, can enumerate for example carbon atom, Siliciumatom, germanium atom, tin atom etc., wherein be preferably carbon atom, Siliciumatom etc., m is 1～5 integer.
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 fork is basic, 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, sila tetramethylene two bases, Silinane two bases etc.
As the concrete compound shown in the general formula (4), at M
1Be zirconium atom, X
1Be 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-two-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 R with 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, sila tetramethylene 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 use in a plurality of mixing.
As being the catalyzer of principal constituent with composition (i), but illustration is by contacting the catalyzer that obtains with composition (i) with active cocatalyst [composition (iii)].
As composition (iii), can all use known material, wherein special preferably clay mineral, clay mineral, aikyiaiurnirsoxan beta, ionic compound, Lewis acid, magnesium chloride, surface treated inorganic oxide or the inorganic halides etc. handled through organic compound.
When making preferred polyethylene-based resin (B), as with the alkene of carbon number more than 3 of ethylene copolymer, but cyclic olefin, divinyl or 1 such as alpha-olefin, norbornylene or norbornadiene such as illustration propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene or vinyl cycloalkane, diene or vinylbenzene such as 4-hexadiene.In addition, also can mix above these alkene of 2 kinds uses.
Macromonomer is meant that end has the olefin polymer of vinyl, be preferably independent polymerising ethylene and the end that obtains have the ethene polymers of vinyl or ethene and carbon number more than 3 olefin-copolymerization and the end that obtains 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, promptly, be derived from the side chain side chain in addition of the alkene of carbon number more than 3, per 1000 main chain mesomethylene carbon, 0.01 of short-chain branches less than and per 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 (promptly
13The above side chain of detected hexyl during C-NMR measures) 0.01 of less than, end has the straight chain shape ethene polymers or the straight chain shape ethylene copolymer of vinyl.
During macromonomer synthetic, as with the alkene of carbon number more than 3 of ethylene copolymer, but cyclic olefin, divinyl or 1 such as alpha-olefin, norbornylene or norbornadiene such as illustration propylene, 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene or vinyl cycloalkane, diene or vinylbenzene such as 4-hexadiene.In addition, also can mix above these alkene of 2 kinds uses.
Use terminal ethene polymers with vinyl or terminal when having the ethylene copolymer of vinyl, (D) number-average molecular weight (M that its straight chain shaped polyethylene converts as macromonomer
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 satisfy formula (1) and/or formula (2), and carry out extruding layer and be pressed into deformation and get significantly difficulty, therefore, might 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, might 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, becoming was difficult to extrude laminating molding, therefore, might can not get layered product.
Manufacture method about the macromonomer among 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, the TOHKEMY 2008-50278 communique to make.
Manufacture method as concrete macromonomer, for example can use with the transistion metal compound [composition (ii)] shown in the following general formula (10) to be the catalyzer of principal constituent, use the method for independent polymerising ethylene or ethene and the olefin-copolymerization of carbon number more than 3 to make.
General formula (10):
The M of composition in (ii)
2Be 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.
The R of composition in (ii)
7And R
8With following general formula (11), (12) or (13) expression, 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 the 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 the general formula (10)
7, R
8The crosslinking group R that is cross-linked to form
9With following general formula (14), (15) or (16) expression, 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
2Be the atom of periodic table of elements IVA family, specifically, can enumerate for example carbon atom, Siliciumatom, germanium atom, tin atom etc., wherein be preferably carbon atom, Siliciumatom, n is 1～5 integer.
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 fork is basic, 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, sila tetramethylene 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-two bases, 1,1,3,3-tetraethyl-sily oxide-1,3-two bases, 1,1,3,3-tetra isopropyl disiloxane-1,3-two bases, 1,1,3,3-tetraphenyl sily oxide-1,3-two bases etc.
As the concrete example of general formula (16), for example can enumerate 1,1-dimethyl-1-sila ethane-1,2-two bases, 1,1-diethyl-1-sila ethane-1,2-two bases, 1,1-di-isopropyl-1-sila ethane-1,2-two bases, 1,1-phenylbenzene-1-sila ethane-1,2-two bases 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 use a plurality of mixing.
As (ii) being the catalyzer of principal constituent, can enumerate that composition is (ii) (iii) contacted the catalyzer that obtains with the active cocatalyst composition with the composition shown in the formula (10).As composition concrete example (iii), about being the catalyzer of principal constituent with composition (i), can enumerate with and the (iii) same material of aforementioned composition 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: use with composition (ii) to the catalyzer of principal constituent with ethene with arbitrarily behind the olefinic polymerization synthetic macromolecule monomer of carbon number more than 3 (1), in the presence of the gained macromonomer, use with the method for composition (i) as catalyzer olefinic polymerization manufacturing polyethylene-based resin (B) more than 3 of principal constituent with ethene and any carbon number; And (2) use with composition (i) and composition (ii) to the catalyzer of principal constituent ethene and the olefinic polymerization of carbon number more than 3 arbitrarily, makes the method for polyethylene-based resin (B) simultaneously at the synthetic of macromonomer.
Polyethylene-based resin (B) is introduced as comonomer by the part of the macromonomer that will use composition and (ii) obtain, thereby becomes the resin that its part has the long-chain side chain.When the molecular weight of general macromonomer was 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 was high, physical strength uprised, but did not generate the long-chain side chain, and processibility reduces.Polyethylene-based resin of the present invention (B) be preferably have long-chain branched structure and number-average molecular weight height, the narrow polyethylene-based resin (B) of molecular weight distribution, have excellent processibility and physical strength height.
The manufacturing 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 make the polyethylene-based resin of excellent particle form.
In the manufacturing of the synthetic and polyethylene-based resin (B) of macromonomer, polymerizing conditions such as polymerization temperature, polymerization time, polymerization pressure, monomer concentration are not particularly limited, polymerization temperature is-100～120 ℃, when considering productivity preferably at 20～120 ℃ and then preferably carry out 60～120 ℃ scope.Polymerization time carries out 10 seconds～20 hours scope 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 use 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 satisfies the condition of above-mentioned (a)～(c) can creating conditions or change of the small-scale of the condition factor and operation respectively arbitrarily according to embodiment described later.Concrete example to condition factor change describes, and the polymerizing conditions such as amount of comonomers that can (ii) adjust the amount of agent with the hydrogen equimolecular quantity of the structure of composition (i), the condition relevant with catalyst component with respect to the amount of composition composition (i) (ii), the kind of employed co-catalyst component etc., polymerization temperature, ethylene partial pressure, coexistence according to employed composition, added are controlled respectively and operated.In addition, also can further make up the scope that enlarges rerum natura with multi-stage polymeric.
More particularly, for example can wait and reduce the terminal ethylenyl groups number by reduction ethylene partial pressure, minimizing comonomer addition, change composition structure (ii).In addition, fusion tension force can prop up chain length, change amount, increase M with respect to composition composition (i) (ii) by change composition structure, the structure that increases terminal ethylenyl groups number, change composition (i), reduction ethylene partial pressure, increase long-chain side chain number, increase long-chain (ii)
w/ M
nWaiting increases.And then, mobile activation energy (E
a) can prop up chain length, control with respect to the amount of composition composition (i) (ii) by composition structure, terminal ethylenyl groups number, the structure of composition (i), ethylene partial pressure, long-chain side chain number, long-chain (ii).
Mixed the new LDPE (film grade) that satisfies above-mentioned condition (A) of specified quantitative and the polyethylene resin composition of polyethylene-based resin (B), good by outward appearance excellence and the processibility of extruding the product that lamination obtains.Polyethylene resin composition of the present invention comprises: 1～50 weight %, be preferably 1～30 weight % and then be preferably 1～20 weight % new LDPE (film grade) (A), 99～50 weight %, be preferably 99～70 weight % and then be preferably 99～80 weight % polyethylene-based resins (B).During the use level less than 1 weight % of new LDPE (film grade) (A), might be difficult to stably extrude laminating molding.On the other hand, when the use level of new LDPE (film grade) (A) surpasses 50 weight %, might 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
3Density is 915～965kg/m
3Scope the time, can take into account the 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 MFR that 2.16kg load (190 ℃) is measured down.When MFR is 3.0～30.0g/10 minute a scope, but thereby the attenuate laminate thickness is stably extruded laminating molding.
Polyethylene resin composition of the present invention is preferably at the fusion tension force (MS of 160 ℃ of mensuration
160) above and then be preferably more than the 40mN for 30mN.Fusion tension force (MS
160) be 30mN when above, can stably extrude laminating molding.
Constitute the lamination of extruding of the present invention and can be respectively a kind or the above mixture of 2 kinds with new LDPE (film grade) (A), the polyethylene-based resin (B) of polyethylene resin composition.
Polyethylene resin composition of the present invention can mix new LDPE (film grade) (A) and polyethylene-based resin (B) dry type to be modulated, carry out the composition that melting mixing can obtain stay in grade by existing known method such as single screw extrusion machine, twin screw extruder, kneader, banbury mixers, so preferred.Consider from the productivity aspect in the middle of these, be generally use single screw extrusion machine or twin screw extruder melting mixing, process for granulating.
Can cooperate known additives such as 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 the polyethylene-based resin of the present invention.In addition, also can mix use with other thermoplastic resins.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 be extruded the laminating molding method by utilization and will form the polyethylene-based resin composition lamination of one deck at least and/or be applied on the various base materials and obtain.Extrude the laminating molding method and can be any of single entry laminating machine, series connection laminating machine, co-extrusion laminating machine, sandwich of layers press, be not particularly limited.In addition, when extruding lamination process,, preferably under 250～350 ℃ temperature, extrude from the mouth mould in order to obtain the good layered product of connectivity of base material and polyethylene-based resin layer.
In addition, the face that contacts with base material at least of the fused films of polyethylene-based resin composition can be by air or oxidation by ozone gas.When utilizing air to carry out oxidizing reaction, it is preferred extruding from the mouth mould under the temperature more than 270 ℃, in addition, when utilizing ozone gas to carry out oxidizing reaction, is preferred extruding more than 250 ℃.In addition, as the treatment capacity of ozone gas, the every 1m that extrudes from the mouth mould
2Film is to be preferred more than the 0.5mg.In addition, in order to improve the connectivity with base material, can carry out known surface treatments such as anchor coating agent processing, Corona discharge Treatment, frame processing, plasma treatment to the junction surface of base material.
As base material, can enumerate synthesising macromolecule copolymer film and thin slice, spin cloth, non-woven fabrics, tinsel, stationery, cellulose film etc.For example formed film of synthesising macromolecule copolymers 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 use printings such as polyurethane series China ink to form.As tinsel, but illustration aluminium foil, Copper Foil etc., and in addition, stationery can be enumerated paperboards such as kraft paper, extensible paper, vellum, glassine paper, cup body paper and developing out paper body paper etc.
Layered product of the present invention can grab a bite for a short time, toilet articles such as backing layer, developing out paper supporter, paper-made vessel and lid, paper ware, release paper and the demoulding tape of drug packagings such as beverage diet product packing, medicine, transfusion band such as desiccating food products, soup, sauce, salted vegetables, sauce, beverage such as instant hand-pulled noodles, shampoo, makeup, diaper, easily use as film, container, tape, supporter in the wide scope such as disassociation property film, half distillation bag made of paper.
Embodiment
Be specifically described for the present invention by the following examples, but the present invention is not limited to this.
Each rerum natura of polyethylene-based resin in synthesis example, embodiment and the 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) measure by gel permeation chromatograph (GPC).Use the HLC-8121GPC/HT of TOSOH Co., Ltd's manufacturing, TSK gelGMHhr-H (20) HT, the column temperature of using TOSOH Co., Ltd to make as post to be set at 140 ℃, elutriant use 1,2 as the GPC device, the 4-trichlorobenzene is measured.Measure the concentration modulation of test portion, inject 0.3mL and measure with 1.0mg/mL.The working curve of molecular weight uses the known polystyrene test portion of molecular weight to proofread and correct.In addition, M
wAnd M
nTry to achieve as the value that the straight chain shaped polyethylene converts.
＜long-chain side chain number 〉
Long-chain side chain number uses VNMRS-400 type nuclear magnetic resonance device that Varian makes, passes through
13C-NMR measures the number of the above long-chain side chain of hexyl.Solvent is tetrachloroethane-d
2As the number of per 1000 main chain mesomethylene carbon, try to achieve by the following formula (4) of record in " Macromolecules " the 31st volume, No. 25,8677～8683 pages (1998).
Long-chain side chain number=IA
α/ (3 * IA
Tot) (4)
[in the formula, IA
αAlpha-carbon peak (chemical shift: integrated intensity 34.6ppm), IA for the long-chain side chain more than the 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. uses Varian to make passes through
13C-NMR measures.Solvent is tetrachloroethane-d
2(chemical shift: number 30ppm), try to achieve by the mean value at the peak by 114ppm, 139ppm as per 1000 main chain mesomethylene carbon for the terminal number of vinyl.In addition, saturated terminal 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 the terminal number (X) of this vinyl and saturated terminal number (Y).
＜density 〉
Density is measured by the density gradient tube method according to JI S K6760 (1995).
<MFR>
MFR measures under 190 ℃, 2.16kg load according to JIS K6760 (1995).
＜fusion tension force 〉
The polyethylene that is used for the mensuration of fusion tension force (MS) is with the IRGANOX1010 that has 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 (the smart mechanism of Japan is made made, trade(brand)name: Laboratory mill), under stream of nitrogen gas, 190 ℃, mixing 3 minutes with rotating speed 30rpm.(the smart mechanism of Japan 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 ° at the capillary viscosimeter of tube diameter 9.55mm for fusion tension force (MS).MS
160For temperature being set at 160 ℃, piston rotation perdurability is that 10mm/ minute, ratio of elongation are set at 47, measures and receives necessary load (mN).MS
190For temperature being set at 190 ℃, piston rotation perdurability is that 10mm/ minute, ratio of elongation are set at 47, measures and receives necessary load (mN).
＜curve inwardly
Polyethylene resin composition is supplied to extruding layer press (the Musashino Kikai Co. of screw rod with 90mm φ, Ltd. forcing machine manufacturing), T die head from A/F 600mm under 315 ℃ temperature is extruded, and the inbound pacing of base material is 200m/ minute, is 50g/m in the weight of paper
2The kraft paper base material on according to extrude resin composition for lamination be the difference of 20 μ m thickness coating width when extruding lamination, T die openings width and polyethylene resin composition as curving inwardly, measure this value.At this moment, compare with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped 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 (Musashino Kikai Co. with 90mm φ screw rod, Ltd. forcing machine manufacturing), T die head from A/F 600mm under 315 ℃ temperature is extruded, and the inbound pacing of base material is 200m/ minute, is 50g/m in the weight of paper
2The kraft paper base material on be that 20 μ m thickness are extruded lamination according to extruding resin composition for lamination.Thereafter, reduce discharge-amount, the laminate thickness of extruding laminating molding that can not carry out the above continous-stable of 100m is measured this value as minimum film thickness.At this moment, compare with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped that the thin situation of minimum film thickness 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 the forcing machine of the extruding layer press (Musashino Kikai Co., Ltd. make) of the screw rod with 90mm φ, and the T die head from A/F 600mm under 315 ℃ temperature is extruded, the outward appearance of visual observation fused films.At this moment, compare with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped 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 screw rod with 90mm φ, Ltd. forcing machine manufacturing), T die head from A/F 600mm under 315 ℃ temperature is extruded, and the inbound pacing of base material is 20m/ minute, is 50g/m in the weight of paper
2The kraft paper base material on be that 20 μ m thickness carry out continuous 500m and extrude laminating molding according to extruding resin composition for lamination.Behind the laminating molding, measure the dirt settling on cooling roller surface.At this moment, compare with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped 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 uses the Miller roller, and the roller cooling temperature is 45 ℃.
And then the manufacturing 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 that uses in the manufacturing of the modulation of modification hectorite, the modulation of catalyzer, polyethylene-based resin etc. all use by previous known method purify, the material of dry, deoxidation.Two (cyclopentadienyl) zirconium dichlorides of dimethylsilane two bases, propane-1, two (cyclopentadienyl) zirconium dichlorides of 3-two 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-two bases, phenylbenzene methylene radical (1-indenyl) (9-fluorenyl) zirconium dichloride use material synthetic by known method, that identify.The hexane solution of triisobutyl aluminium (0.714M) uses Tosoh FinechemCorporation to make.
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, add N in gained solution, N-dimethyl-stearylamine 330g (1.1mol) is heated to 60 ℃, thus modulation hydrochloride solution.In this solution, add hectorite 1kg.With this suspension under 60 ℃, stirred 3 hours, remove supernatant liquor after, wash with 60 ℃ water 50L.Thereafter, at 60 ℃, 10
-3Torr dry 24 hours down pulverizes with airflow milling, thereby obtains 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 the 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, after stirring 3 hours under 60 ℃, leave standstill and remove supernatant liquor, and then the hexane solution (0.15M) of interpolation triisobutyl aluminium, make catalyst precursor slurry (100g/L).
In above-mentioned synthetic catalyst precursor slurry, 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 stirred 6 hours.Leave standstill and remove supernatant liquor, and then add the hexane solution (0.15M) of triisobutyl aluminium, finally obtain the catalyst pulp of 100g/L.
[manufacturing of polyethylene-based resin (B-1)]
In the polymerizer of 540 liters of internal volumes, import 5.9 liters of 300 liters of hexanes and 1-butylene, the interior temperature of autoclave is warming up to 70 ℃.Add aforementioned catalyzer (p) 120 milliliters in this autoclave, importing ethene/hydrogen gas mixture (hydrogen 500ppm) is 0.9MPa until dividing potential drop, the beginning polymerization.In the polymerization, import ethene/hydrogen gas mixture (hydrogen 500ppm) continuously so that dividing potential drop is remained 0.9MPa.In addition, polymerization temperature is controlled to be 70 ℃.After polymerization began after 90 minutes the interior pressure-off of aggregation container pressed, filtering content thing, drying obtained 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 per 1000 carbon atoms are 0.13, MS
190Be 22mN, MS
160Be 34mN.
In addition, in this Production Example, carry out the manufacturing of the macromonomer shown in the following reference example 1 and under the coexistence of this macromonomer, carry out the manufacturing of polyethylene-based resin (B-1) by ethene and 1-butylene copolymerization.
Reference example 1
[manufacturing of macromonomer]
Replace catalyzer (p) and add the modulation of synthesis example 1[catalyzer (p)] in 120 milliliters in synthetic catalyst precursor slurry, in addition, with with the manufacturing of 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
[manufacturing 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 synthetic catalyzer (p), replace ethene/hydrogen gas mixture and only use ethene, in addition, with with the manufacturing of 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, per 1000 carbon atoms of long-chain side chain number are 0.13, MS
190Be 24mN, MS
160Be 38mN.
In addition, in this Production Example, carry out the manufacturing of the macromonomer shown in the following reference example 2 and under the coexistence of this macromonomer, carry out the manufacturing of polyethylene-based resin (B-1) by ethene and 1-butylene copolymerization.
Reference example 2
[manufacturing of macromonomer]
Replace catalyzer (p) and add the modulation of synthesis example 1[catalyzer (p)] in 131 milliliters in synthetic catalyst precursor slurry, in addition, with with the manufacturing of 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 with the modulation of synthesis example 1[catalyzer (p)] same method modulates, and obtains the catalyst pulp of 100g/L.
[manufacturing 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 with the manufacturing of 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, per 1000 carbon atoms of long-chain side chain number are 0.10, MS
190Be 44mN, MS
160Be 66mN.
In addition, in this Production Example, carry out the manufacturing of the macromonomer shown in the following reference example 3 and under the coexistence of this macromonomer, carry out the manufacturing of polyethylene-based resin (B-3) by ethene and 1-butylene copolymerization.
Reference example 3
[manufacturing of macromonomer]
Replace catalyzer (q) and add the modulation of synthesis example 3[catalyzer (q)] in 106 milliliters in synthetic catalyst precursor slurry, in addition, with with the manufacturing of 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-two bases, in addition, use modulation with synthesis example 1[catalyzer (p)] same method modulates, and obtains the catalyst pulp of 100g/L.
[manufacturing 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 with the manufacturing of 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, per 1000 carbon atoms of long-chain side chain number are 0.12, MS
190Be 27mN, MS
160Be 40mN.
In addition, in this Production Example, carry out the manufacturing of the macromonomer shown in the following reference example 4 and under the coexistence of this macromonomer, carry out the manufacturing of polyethylene-based resin (B-4) by ethene and 1-butylene copolymerization.
Reference example 4
[manufacturing of macromonomer]
Replace catalyzer (r) and add the modulation of synthesis example 4[catalyzer (r)] in 133 milliliters in synthetic catalyst precursor slurry, in addition, with with the manufacturing of 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 with the modulation of synthesis example 1[catalyzer (p)] same method modulates, and obtains the catalyst pulp of 100g/L.
[manufacturing 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 at 60 ℃, in addition, with with the manufacturing of 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, per 1000 carbon atoms of long-chain side chain number are 0.10, MS
190Be 49mN, MS
160Be 70mN.
In addition, in this Production Example, carry out the manufacturing of the macromonomer shown in the following reference example 5 and under the coexistence of this macromonomer, carry out the manufacturing of polyethylene-based resin (B-5) by ethene and 1-butylene copolymerization.
Reference example 5
[manufacturing of macromonomer]
Replace catalyzer (s) and add the modulation of synthesis example 5[catalyzer (s)] in 135 milliliters in synthetic catalyst precursor slurry, in addition, with with the manufacturing of 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 with synthesis example 1[modification hectorite] in synthetic modification hectorite 500g be suspended in 1.8 liters of the hexanes, 2.9 liters of the hexane solutions (0.714M) of interpolation triisobutyl aluminium, stirring is 1 hour under the room temperature, thereby obtains the product of contact of modification hectorite and triisobutyl aluminium.On the other hand, add that two (cyclopentadienyl) zirconium dichloride 6.97g (20mmol) of dimethylsilane two bases are dissolved in the material that toluene obtains, stir an evening under the room temperature, thereby obtain catalyst pulp (100g/L).
[manufacturing 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 at 1.2MPa, polymerization temperature is controlled at 85 ℃, in addition, use manufacturing 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.
[manufacturing of polyethylene-based resin (B-6)]
In the polymerizer of 540 liters of the internal volumes of the macromonomer that contains above-mentioned manufacturing, import 0.75 liter of the 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 ℃.Import ethene/hydrogen gas mixture (hydrogen 22000ppm) and make that dividing potential drop is 0.2MPa, the beginning polymerization.In the polymerization, import ethene/hydrogen gas mixture continuously and make dividing potential drop remain 0.2MPa.In addition, polymerization temperature is controlled at 85 ℃.After polymerization begins 90 minutes, after the interior pressure-off pressure with autoclave, the suction filtration content.After the 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, per 1000 carbon atoms of long-chain side chain number are 0.15, MS
190Be 21mN, MS
160Be 30mN.
Synthesis example 7
[manufacturing of polyethylene-based resin (B-7)]
Do not add 1-butylene, in addition, use manufacturing 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, per 1000 carbon atoms of long-chain side chain number are 0.12, MS
190Be 30mN, MS
160Be 55mN.
The characteristic of the characteristic of the macromonomer in the synthesis example 1～7 and polyethylene-based resin (B-1)～(B-7) is shown in table 1.
The characteristic of the new LDPE (film grade) that uses in following embodiment and the comparative example is shown in table 2.
[table 2]
Embodiment 1
The new LDPE (film grade) that obtains with the high-pressure free radical polymerization by the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) (below, be called (A-1).) behind polyethylene-based resin (B-3) the 85 weight % shown in the 15 weight %, synthesis example 3, be adjusted to 180 ℃ single screw extrusion machine (PLACOCO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd makes; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) behind polyethylene-based resin (B-2) the 95 weight % shown in (A-2) 5 weight %, the synthesis example 2, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-2) the 50 weight % shown in (A-1) 50 weight %, the synthesis example 2, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd makes; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) behind polyethylene-based resin (B-1) the 85 weight % shown in (A-2) 15 weight %, the synthesis example 1, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-4) the 75 weight % shown in (A-1) 25 weight %, the synthesis example 4, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-5) the 90 weight % shown in (A-1) 10 weight %, the synthesis example 5, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-6) the 97.5 weight % shown in (A-1) 2.5 weight %, the synthesis example 6, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd makes; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) behind polyethylene-based resin (B-7) the 92.5 weight % shown in (A-2) 7.5 weight %, the synthesis example 7, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene217 that TOSOH Co., Ltd makes; Density 923kg/m
3, MFR4.5g/10 minute, MS
160160mN) behind polyethylene-based resin (B-4) the 75 weight % shown in (A-3) 25 weight %, the synthesis example 4, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene3MO4A that TOSOH Co., Ltd makes; Density 924.5kg/m
3, MFR4.5g/10 minute, MS
160110mN) behind polyethylene-based resin (B-4) the 75 weight % shown in (A-4) 25 weight %, the synthesis example 4, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-3) the 99.5 weight % shown in (A-1) 0.5 weight %, the synthesis example 3, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 lamination, compare to curve inwardly with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped and become big, for bad.
Comparative example 2
The new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-3) the 45 weight % shown in (A-1) 55 weight %, the synthesis example 3, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 was extruded lamination, comparing can't be with the minimum film thickness attenuation, for bad with high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped.
Comparative example 3
The new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd makes; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) behind polyethylene-based resin (B-2) the 99.5 weight % shown in (A-2) 0.5 weight %, the synthesis example 2, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 lamination, compare to curve inwardly with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped and become big, for bad.
Comparative example 4
The new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) behind polyethylene-based resin (B-2) the 45 weight % shown in (A-1) 55 weight %, the synthesis example 2, be adjusted to 180 ℃ single screw extrusion machine (PLACO CO. at barrel zone temperature, LTD. make, 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 extruding laminating molding, 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 lamination, compare with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped and to make the minimum film thickness attenuation, for bad.
Comparative example 5
The new LDPE (film grade) that obtains by the high-pressure free radical polymerization with the tumbler mixer ready-mixed (the trade(brand)name Petrothene205 that TOSOH Co., Ltd makes; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) (A-2) 15 weight %, straight chain shape new LDPE (film grade) (the trade(brand)name Nipolon Z 04P66A that TOSOH Co., Ltd makes that obtains by the metallocene series catalysts; Density 917kg/m
3, MFR15g/10 minute) (C-1) behind the 85 weight %, be adjusted to melting mixing, granulation in 180 ℃ the single screw extrusion machine (PLACO CO., LTD. makes, pattern PDA-50) 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 extruding laminating molding, 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 lamination, only obtain identical the curving inwardly of high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that 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 new LDPE (film grade) (the trade(brand)name Petrothene205 that TOSOH Co., Ltd makes that obtains by the high-pressure free radical polymerization; Density 924kg/m
3, MFR3g/10 minute, MS
160160mN) (A-2) 100 weight % carry out laminating molding.
Measure MS, when extruding laminating molding, 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 new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) 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) the 100 weight % shown in the synthesis example 4 are carried out laminating molding.
Measure MS, when extruding laminating molding, 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, compare with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) that the same terms laminated is shaped to curve inwardly greatly, for bad.
Comparative example 8
According to the method shown in the evaluation method of polyethylene-based resin, to straight chain shape new LDPE (film grade) (the trade(brand)name Nipolon-Z 04P66A that TOSOH Co., Ltd makes that obtains by the metallocene series catalysts; Density 917kg/m
3, the MFR15g/10 branch) (C-1) 100 weight % carry out laminating molding.
Measure MS, attempt extruding laminating molding, because the fused film instability 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 identical performance of estimating down with the same terms of high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes).
Comparative example 9
According to the method shown in the evaluation method of polyethylene-based resin, to new LDPE (film grade) (the trade(brand)name Petrothene360 that TOSOH Co., Ltd makes that obtains by the high-pressure free radical polymerization; Density 919kg/m
3, MFR1.6g/10 minute, MS
160295mN) (A-1) 100 weight % carry out laminating molding.
Measure MS, attempt extruding laminating molding, 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 identical performance of estimating down with the same terms of high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes).
Comparative example 10
According to the method shown in the evaluation method of polyethylene-based resin, to new LDPE (film grade) (the trade(brand)name Petrothene217 that TOSOH Co., Ltd makes that obtains by the high-pressure free radical polymerization; Density 923kg/m
3, MFR4.5g/10 minute, MS
160160mN) (A-3) 100 weight % carry out laminating molding.
Measure MS, when extruding laminating molding, 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 new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) 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 new LDPE (film grade) (the trade(brand)name Petrothene3M04A that TOSOH Co., Ltd makes that obtains by the high-pressure free radical polymerization; Density 924.5kg/m
3, MFR4.5g/10 minute, MS
160110mN) (A-4) 100 weight % carry out laminating molding.
Measure MS, when extruding laminating molding, 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, the pollution on cooling roller surface with the high-pressure process new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes) of the same terms laminated shaping, curve inwardly big, 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 new LDPE (film grade) (the trade(brand)name Petrothene203 that TOSOH Co., Ltd makes that obtains by the high-pressure free radical polymerization; Density 919kg/m
3, MFR8g/10 minute, MS
16070mN) (A-5) 100 weight % carry out laminating molding.
Measure MS, when extruding laminating molding, 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 (6)
1. polyethylene resin composition, it is characterized in that it comprises: the density that obtains by the high-pressure free radical polymerization is 915～935kg/m
3, melt mass flow rate that 2.16kg load (190 ℃) is measured down (below, be called MFR.) be 0.5～5.0g/10 minute new LDPE (film grade) (A) 1～50 weight %; And polyethylene-based resin (B) 99～50 weight % that satisfy 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 per 1000 carbon atom,
(c) at the fusion tension force (MS of 190 ℃ of mensuration
190) (mN) and at the following MFR (g/10 minute) that measures of 2.16kg load (190 ℃) satisfy following formula (1)
MS
190＞22×MFR
-0.88 (1)
And fusion tension force (MS 160 ℃ of mensuration
160) (mN) and at the following MFR (g/10 minute) that measures of 2.16kg load (190 ℃) satisfy following formula (2)
MS
160＞110-110×log(MFR) (2)。
2. polyethylene resin composition according to claim 1, it is characterized in that, in the presence of macromonomer, or in synthetic this macromonomer, with ethene and arbitrarily carbon number more than 3 olefinic polymerization and the polyethylene-based resin that obtains uses as polyethylene-based resin (B)
Described macromonomer has the ethylene copolymer that the ethene polymers of vinyl or the olefin-copolymerization more than 3 obtains with ethene and carbon number end have a vinyl by the end that obtains by polymerising ethylene and constitutes, and, described 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.
3. polyethylene resin composition according to claim 1 and 2 is characterized in that, satisfies the condition of following (f)～(h):
(f) density is 915～965kg/m
3
(g) MFR that measures down at 2.16kg load (190 ℃) be 3.0～30.0g/10 minute,
(h) at the fusion tension force (MS of 160 ℃ of mensuration
160) be more than the 30mN.
4. according to claim 1 or 2 described polyethylene resin compositions, it is characterized in that, be used to extrude lamination.
5. a layered product is characterized in that, it has the above layer that is formed by claim 1 or 2 described polyethylene resin compositions of one deck at least.
6. according to claim 1 or the 2 described lamination polyethylene resin compositions of extruding, it is characterized in that the fusion tension force (MS that uses 160 ℃ of mensuration
160) be the above new LDPE (film grade) (A) of 150mN.
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| CN110431179A (en) * | 2017-03-28 | 2019-11-08 | 东曹株式会社 | Resin combination and the film formed by it |
| CN111356737A (en) * | 2017-12-12 | 2020-06-30 | 日本聚乙烯株式会社 | Polyethylene resin composition for lamination, laminate, and method for producing laminate |
| CN112673064A (en) * | 2018-09-12 | 2021-04-16 | 东曹株式会社 | Polyethylene resin composition, laminate, and medical container |
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| JP5707848B2 (en) * | 2010-10-21 | 2015-04-30 | 東ソー株式会社 | Foamed laminate for microwave cooking |
| JP2012136666A (en) * | 2010-12-27 | 2012-07-19 | Tosoh Corp | Polyethylene resin composition for extrusion laminate and laminated body |
| JP2012136665A (en) * | 2010-12-27 | 2012-07-19 | Tosoh Corp | Ethylenic polymer composition for extrusion lamination, and laminated body |
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| JP5825023B2 (en) * | 2011-09-30 | 2015-12-02 | 東ソー株式会社 | Laminated body |
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| JP5895483B2 (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 |
| JP6772444B2 (en) * | 2015-09-25 | 2020-10-21 | 日本ポリエチレン株式会社 | Resin composition for film and film |
| BR112018015379B1 (en) * | 2016-02-12 | 2022-07-19 | Dow Global Technologies Llc | FOUNDRY FILM, LAMINATE AND ARTICLE |
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2009
- 2009-04-16 TW TW098112624A patent/TWI427114B/en active
- 2009-04-17 JP JP2009100888A patent/JP5299050B2/en active Active
- 2009-05-07 CN CN2009101376764A patent/CN101575430B/en active Active
- 2009-05-07 KR KR1020090039633A patent/KR20090117629A/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| CN108357116A (en) * | 2017-01-27 | 2018-08-03 | 加川清二 | The manufacturing device of fragility plastic foil |
| CN108357116B (en) * | 2017-01-27 | 2020-04-03 | 加川清二 | Apparatus for manufacturing cracked plastic film |
| CN110431179A (en) * | 2017-03-28 | 2019-11-08 | 东曹株式会社 | Resin combination and the film formed by it |
| CN111356737A (en) * | 2017-12-12 | 2020-06-30 | 日本聚乙烯株式会社 | Polyethylene resin composition for lamination, laminate, and method for producing laminate |
| CN110105647A (en) * | 2018-04-13 | 2019-08-09 | 株式会社旭包装 | The manufacturing method of polyethylene sheets, composite sheet and polyethylene sheets |
| CN112673064A (en) * | 2018-09-12 | 2021-04-16 | 东曹株式会社 | Polyethylene resin composition, laminate, and medical container |
| CN112673064B (en) * | 2018-09-12 | 2023-10-13 | 东曹株式会社 | Polyethylene resin composition, laminate, and medical container |
| US11884799B2 (en) | 2018-09-12 | 2024-01-30 | Tosoh Corporation | Polyethylene resin composition, laminate, and medical container |
| CN113717451A (en) * | 2020-05-22 | 2021-11-30 | 韩华道达尔有限公司 | Polyethylene resin composition and separation membrane for secondary battery prepared from same |
| CN113717451B (en) * | 2020-05-22 | 2023-11-28 | 韩华道达尔能源有限公司 | Polyethylene resin composition and separation film for secondary battery prepared from same |
| CN116162300A (en) * | 2021-11-25 | 2023-05-26 | 旭化成株式会社 | Ethylene resin composition and molded article |
| CN116162300B (en) * | 2021-11-25 | 2024-08-09 | 旭化成株式会社 | Ethylene resin composition and molded article |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201000541A (en) | 2010-01-01 |
| KR20090117629A (en) | 2009-11-12 |
| CN101575430B (en) | 2013-05-15 |
| JP5299050B2 (en) | 2013-09-25 |
| TWI427114B (en) | 2014-02-21 |
| JP2009293014A (en) | 2009-12-17 |
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