CN101100524B - Film and producing method theroef - Google Patents
Film and producing method theroef Download PDFInfo
- Publication number
- CN101100524B CN101100524B CN2007101388739A CN200710138873A CN101100524B CN 101100524 B CN101100524 B CN 101100524B CN 2007101388739 A CN2007101388739 A CN 2007101388739A CN 200710138873 A CN200710138873 A CN 200710138873A CN 101100524 B CN101100524 B CN 101100524B
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- CN
- China
- Prior art keywords
- film
- ethene
- vinyl polymer
- molecular weight
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 41
- 238000000465 moulding Methods 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 239000004711 α-olefin Substances 0.000 claims description 28
- 238000009826 distribution Methods 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 18
- 230000008018 melting Effects 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 28
- 229920001577 copolymer Polymers 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000003054 catalyst Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002002 slurry Substances 0.000 description 18
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 17
- 238000004519 manufacturing process Methods 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 238000001125 extrusion Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 10
- 238000005259 measurement Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- -1 1-dodecylene Natural products 0.000 description 9
- 150000002899 organoaluminium compounds Chemical class 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- 238000012856 packing Methods 0.000 description 8
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 7
- 238000012685 gas phase polymerization Methods 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011859 microparticle Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000013519 translation Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002152 alkylating effect Effects 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 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
- 239000012925 reference material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- ZEJOAJDTTUTKSZ-UHFFFAOYSA-N 2,4,6-tris(fluoromethyl)phenol Chemical compound OC1=C(CF)C=C(CF)C=C1CF ZEJOAJDTTUTKSZ-UHFFFAOYSA-N 0.000 description 1
- XNQLVVSDYOHIND-UHFFFAOYSA-N 3,4,5-tris(fluoromethyl)phenol Chemical compound FCC=1C=C(C=C(C1CF)CF)O XNQLVVSDYOHIND-UHFFFAOYSA-N 0.000 description 1
- HJSSBIMVTMYKPD-UHFFFAOYSA-N 3,5-difluorophenol Chemical compound OC1=CC(F)=CC(F)=C1 HJSSBIMVTMYKPD-UHFFFAOYSA-N 0.000 description 1
- UGEJOEBBMPOJMT-UHFFFAOYSA-N 3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1 UGEJOEBBMPOJMT-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical class C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- PEMDHCGOAOHYTL-UHFFFAOYSA-N C=CCCCC.CC1=C(C=C(C(=O)O)C=C1)C(=O)O Chemical compound C=CCCCC.CC1=C(C=C(C(=O)O)C=C1)C(=O)O PEMDHCGOAOHYTL-UHFFFAOYSA-N 0.000 description 1
- NZDLIIBVQQCHBI-UHFFFAOYSA-L Cl[Zr]Cl.CC1=C[CH]C=C1 Chemical class Cl[Zr]Cl.CC1=C[CH]C=C1 NZDLIIBVQQCHBI-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NKKALSOFYFMKGW-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] Chemical class [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] NKKALSOFYFMKGW-UHFFFAOYSA-L 0.000 description 1
- DJLLJBLGCMFLSC-UHFFFAOYSA-N [dimethyl-(silylamino)silyl]methane Chemical compound C[Si](C)(C)N[SiH3] DJLLJBLGCMFLSC-UHFFFAOYSA-N 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
-
- 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
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A film obtaining through moulding vinyl polymer is disclosed. The vinyl polymer comprises monomer unit based on ethylene and monomer unit based on Alpha-alkene which contains 3 to 20 carbon atoms, wherein the relation of the molecular weight distributing of the film [Mw/Mn]b and the one of the film after 205 hours sunlight carbon arc lamp exposure processing [Mw/Mn]a meets the following formula (1): 0.6 <[Mw/Mn]a/[Mw/Mn]b<1.2 (1).
Description
Technical field
The film that the present invention relates to have excellent weather resistance, this film obtains by the molding vinyl polymer, relates to the method for producing this film simultaneously.
Background technology
The film that obtains by molding vinyl polymers such as blow moulding, T-die head casting (for example ethene-alpha-olefin copolymer, the Low Density Polyethylene of high-pressure process) is as various packing films, as explanation book pocket, heavily loaded bag, wrap film be used for the former film of laminating material.For example, well-known following film: by the film that ethene and 4-methyl-1-pentene are made through the multipolymer of the 2-stage polymerization acquisition of regulation, this 2-stage polymerization uses two (methyl cyclopentadienyl) zirconium dichlorides as catalyst component (for example JP-A-3-234717); By the film that the blowing of resin combination experience is obtained, this resin combination is formed (for example JP-A-6-65443) etc. by the multipolymer and the high-pressure process Low Density Polyethylene that use two (n-butyl cyclopentadienyl) zirconium dichlorides as catalyst component ethene and 1-hervene copolymer to be prepared.
Yet when being used for by the film that conventional vinyl polymer molding obtains extending to for such as the coverture in agricultural-food such as plastic green house cultivation, plastic canopy cultivation cultivation place the time, film strength is deterioration sometimes.Therefore, conventional film not necessarily satisfies a small amount of deterioration of the intensity that is caused by extension, i.e. weathering resistance.
Summary of the invention
In this case, the order of the present invention method that provides the film that has excellent weather resistance and produce this film.
A first aspect of the present invention relates to the film that obtains by the molding vinyl polymer, and this vinyl polymer has based on the monomeric unit of ethene with based on the monomeric unit of the alpha-olefin with 3～20 carbon atoms, the molecular weight distribution of wherein said film [Mw/Mn]
bWith the molecular weight distribution [Mw/Mn] of described film through 250 hours daylight carbon arc lamp exposure-processed caudacorias
aSatisfy the relation of following formula (1):
0.6＜[Mw/Mn]
a/[Mw/Mn]
b＜1.2 (1)
A second aspect of the present invention relates to the method for preparing film, be included in and satisfy following all conditions (i)～(molding vinyl polymer resins film forming under the condition v), this vinyl polymer resins has based on the monomeric unit of ethene with based on the monomeric unit of the alpha-olefin with 3～20 carbon atoms, draws amount M (kg/hr), die lip area A (mm that speed V (m/min), resin extrude from die lip under the described conditions
2) and die lip width W (mm) satisfy following formula (2):
(i) melt flow rate (MFR) is 0.01～10g/10min,
(ii) density (d) is 890～970kg/m
3,
(iii) fluid-activated can (Ea) be 50kJ/mol or bigger,
(iv) molecular weight distribution (Mw/Mn) be 3～25 and
(it is 3 or still less that flex point number on the melting curve between the temperature is finished in v) obtain by dsc 25 ℃ and fusion.
20＜V/(M/A)×W)＜150 (2)
Embodiment
Vinyl polymer is to contain based on ethylene monomer unit with based on the multipolymer of the 'alpha '-olefin monomers unit with 3～20 carbon atoms.
Example with alpha-olefin of 3～20 carbon atoms comprises propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecylene, 4-methyl-1-pentene and 4-methyl isophthalic acid-hexene, they can use separately, or two or more are used in combination.Combination and 4-methyl-1-pentene as alpha-olefin, 1-hexene, 1-butylene and 1-hexene are preferred, and in addition, the 1-hexene is preferred.
Be used for vinyl polymer of the present invention, the monomeric unit content of derived from ethylene is 50～99.5wt%, based on the gross weight (100wt%) of vinyl polymer.In addition, be 0.5～50wt% derived from the monomeric unit content of the alpha-olefin with 3～20 carbon atoms, based on the gross weight (100wt%) of vinyl polymer.
In the scope of not damaging effect of the present invention, be used for vinyl polymer of the present invention and also can contain derived from except ethene with have the monomeric unit of other monomer the alpha-olefin of 3～20 carbon atoms.The example of other monomer comprises conjugated diolefine (for example divinyl, isoprene), non-conjugated diene (for example 1,4-pentadiene), vinylformic acid, acrylate (for example methyl acrylate, ethyl propenoate), methacrylic acid, methacrylic ester (for example methyl methacrylate, Jia Jibingxisuanyizhi) and vinyl-acetic ester.
The example that is used for vinyl polymer of the present invention comprises ethene-1-hexene copolymer, ethene-1-octene copolymer, ethene-1-butylene-1-hexene copolymer, ethene-1-butylene-4 methyl 1 pentene copolymer and ethene-1-butylene-1-octene copolymer, optimal ethylene-1-hexene copolymer, ethene-1-butylene-1-hexene copolymer and ethene-1-butylene-4 methyl 1 pentene copolymer, more preferably ethene-1-hexene copolymer and ethene-1-butylene-1-hexene copolymer.
Consider and improve weathering resistance and mouldability, the melt flow rate (MFR) (MFR, the g/10min of unit) that is used for vinyl polymer of the present invention is 0.01g/10min or bigger preferably, more preferably 0.05g/10min or bigger, further preferred 0.1g/10min or bigger.On the other hand, consider the physical strength that improves film, MFR is 10g/10min or littler preferably, more preferably 7g/10min or littler, further preferred 5g/10min or littler, preferred especially 3g/10min or littler.MFR is the value of measuring down at 190 ℃ of load 21.18N (2.16Kg) according to the A-method among the JIS K7210-1995.
In addition, vinyl polymer has 890～970kg/m
3Density, consider the rigidity of improving film, density is 900kg/m preferably
3Or bigger, more preferably 905kg/m
3Or bigger, further preferred 910kg/m
3Or it is bigger.On the other hand, consider the shock strength of improving film, density is 940kg/m preferably
3Or littler, more preferably 930kg/m
3Or it is littler.The density of multipolymer is measured according to the A-method among the JISK7112-1980 after according to JIS K6760-1995 annealing.
Be used for vinyl polymer of the present invention and have long chain branched, compare with conventional linear ethylene based polyalcohol preferably have high fluid-activated can (Ea; The kJ/mol of unit).The Ea of conventional multipolymer is lower than 50kJ/mol, therefore, can not obtain enough satisfactory degrees sometimes aspect weathering resistance and the mouldability.
Consider and improve weathering resistance and mouldability, the Ea that is used for vinyl polymer of the present invention is preferably 55kJ/mol or bigger, more preferably 60kJ/mol or bigger.In addition, consider the enhancing transparency, it is 100kJ/mol or littler preferably, more preferably 90kJ/mol or littler.
Above-mentioned Ea is by the shift factor (a in the master curve preparation according to the Arrhenius equation
T) numerical value that calculates, based on the melt complex viscosity (η of temperature-this curve display of time superposition theorem at 190 ℃; The Pa s of unit) diagonal frequencies (ω; The rad/s of unit) dependency, and Ea is the value that can measure by the following method.
Namely at the temperature (T of 130 ℃, 150 ℃, 170 ℃ and 190 ℃, unit is ℃) under, melt complex viscosity-radian frequency the curve of each ethene-alpha-olefin copolymer is superimposed upon on the curve of ethene-alpha-olefin copolymer melt complex viscosity-radian frequency based on temperature-time superposition theorem for each comfortable 190 ℃, obtains the shift factor (a of each temperature (T)
T), then, calculate [In (a by each temperature and the shift factor when each temperature respectively by method of least squares
T)] and the linear-apporximation equation of [1/ (T+273.16)] (following equation (I)).Next, determine Ea by slope m and the following equation (II) of linear equation.
In(a
T)＝m(1/(T+273.16))+n (I)
Ea＝|0.008314×m| (II)
a
T: shift factor
Ea: fluid-activated can (unit: kJ/mol)
T: temperature (unit: ℃)
Above-mentioned calculating can use commercially available computer software to determine, the software that can list is Rhinos V.4.4.4 (Rheometrics Limited manufacturing) for example.
Wherein, shift factor (a
T) be translational movement, wherein the double logarithmic curve of the melt complex viscosity-radian frequency of each temperature to log (Y)=-the direction translation (Y-axis: melt complex viscosity of log (X) axle, X-axis: radian frequency), thereby be superimposed upon on 190 ℃ the curve of melt complex viscosity-radian frequency, in this stack, each double logarithmic curve of the melt complex viscosity-radian frequency under the temperature translation a on radian frequency separately
TTranslation 1/a doubly and on the melt complex viscosity
TDoubly.In addition, when equation (I) is determined by method of least squares by 4 point values of 130 ℃, 150 ℃, 170 ℃ and 190 ℃, relation conefficient normally 0.99 or bigger.
The measurement of melt complex viscosity-radian frequency curve uses viscoelasticity measurement instrument (Rheometrics mechanical spectrometer RMS-800 for example, by Rheometrics, Limited makes) to carry out under following condition usually:
(1) geometry: parallel plate,
(2) board diameter: 25mm,
(3) distance between plates: 1.5～2mm,
(4) tension force: 5% and
(5) radian frequency: 0.1～100rad/s
In addition, measure and in nitrogen atmosphere, carry out, preferably add an amount of antioxidant (for example 1000wt-ppm) in advance in sample.
Consider and improve mouldability, especially reduce and extrude load that ethene-alpha-olefin copolymer of the present invention preferably has 3 or bigger molecular weight distribution, more preferably 5 or bigger, more preferably 6 or bigger and most preferably 7 or bigger.On the other hand, consider the physical strength of the moulded parts that enhancing will obtain, molecular weight distribution preferably 25 or littler, more preferably 20 or littler, most preferably 15 or littler.
Above-mentioned molecular weight distribution is the weight-average molecular weight that is transformed into the polystyrene molecular weight separately (Mw) and the number-average molecular weight (Mn) that is obtained by above-mentioned gel permeation chromatography measurement by calculating, and Mw is divided by the value of Mn (Mw/Mn) back acquisition.
In addition, as measuring condition, illustrate for example following condition:
(1) device: Waters 150C (being made by Waters limited)
(2) separator column: TOSOH TSKgelGMH6-HT
(3) measure temperature: 140 ℃
(4) carrier: orthodichlorobenzene
(5) flow: 1.0ml/min
(6) injection rate: 500 μ L
(7) detector: differential refraction
(8) reference material of molecular weight: polystyrene standard
Consider to strengthen weathering resistance and transparency, be used for the melting curve that vinyl polymer of the present invention preferably obtains by dsc and have 3 or flex point still less in temperature range between the temperature is finished in 25 ℃ and fusion.If the flex point number is many, mean and have other melting peak or the acromion except maximum melting peak (melting peak with climax height) in a large number on the melting curve of vinyl polymer, therefore mean in vinyl polymer, to have the polymeric constituent that has different monomers unit content in a large number, and the composition of ethene-alpha-olefin copolymer distribution (namely being included in the monomeric unit content distribution of the polymeric constituent in the ethene-alpha-olefin copolymer) is wide.Here the flex point of mentioning refers to melting curve from concave surface to convex surface or the transition point from convex surface to concave surface.
The number of maximum fusing point (Tm) and melting curve flex point can be determined by the melting curve that for example following method uses dsc to measure the vinyl polymer acquisition:
Use differential scanning calorimeter (for example by Perkin Elmer Co., the differential scanning calorimeter DSC-7 type that Ltd. makes), for example, will wrap up the aluminium dish of about 10mg sample:
(1) sample melted is finished 20 ℃ of temperature or higher temperature kept 5 minutes being higher than,
(2) with the speed of 5 ℃/min, the temperature that keeps from (1) is cooled to 20 ℃,
(3) 20 ℃ kept 5 minutes and
(4) finish the about 20 ℃ temperature of temperature from 20 ℃ of heated sample to the fusion that is higher than sample with the speed of 5 ℃/min.
The flex point number of maximum fusing point (Tm) and melting curve determines that by measuring the differential scanning measurement curve that obtains in (4) namely Tm is defined as the temperature at curve maximum peak place.
Consider the improvement of weathering resistance and mouldability, the melt flow rate (MFR) that is used for vinyl polymer of the present invention is preferably 60 or bigger than (MFRR).MFRR is the melt flow rate value measured under 190 ℃, 211.82N (21.60kg) load according to JIS K7210-1995 (MFR-H, unit: the g/10min) value that obtains divided by the MFR that measures under 190 ℃, 21.18N (2.16kg) load according to JIS K7210-1995.For the measurement of above-mentioned melt flow rate (MFR), use usually to the polymkeric substance that wherein adds the antioxidant of about 1000wt-ppm in advance.
Comprise the method for therein ethylene and alpha-olefin copolymerization under ingredient of solid catalyst suitably as the method for the production of vinyl polymer of the present invention, this ingredient of solid catalyst obtains by catalyst component is loaded on the microparticle support.For example, when using metallocene (transistion metal compound with cyclopentadienyl type anion frame), can use the promotor for preparing by load compound (for example organo-aluminium compound, boride and organic zinc compound), this compound can form ionic complex by the ionized metal metallocene complex.
As microparticle support, preferred porous material, and can use inorganic oxide such as SiO
2, Al
2O
3, MgO, ZrO
2, TiO
2, B
2O
3, CaO, ZnO, BaO and ThO
2Clay and clay mineral if you would take off stone, polynite, hectorite, raponite and saponite; With organic polymer such as polyethylene, polypropylene and styrene diethylene benzene copoly mer.
50% volume of microparticle support-median size is 10～500 μ m normally, and this 50% volume-median size is measured by the light scattering type laser diffractometry.In addition, the micro pore volume of microparticle support is 0.3～10ml/g normally, and micro pore volume is mainly measured by gas adsorption method (BJH method).The specific surface area of microparticle support is 10～1000m normally
2/ g, and it is measured by gas adsorption method (BET method).
The production method of the vinyl polymer of Shi Yonging in the present invention, be included in the method for the following copolymerization of ethylene of polymerizing catalyst existence and alpha-olefin, described polymerizing catalyst is by making following promotor carrier (A), have the metallocene (B) of part and organo-aluminium compound (C) contact prepares, and described part has two cyclopentadienyl type anion frames by such as the bridged group of alkylidene group or silicylene structure connected to one another.
Above-mentioned promotor carrier (A) be by make zinc ethyl as component (a), as two kinds of component (b) fluoridize phenol, as the water of component (c), as the inorganic particles shape carrier of component (d) with as the trimethyldisilazane (((CH of component (e)
3)
3) Si)
2NH) contact and the carrier of acquisition.
The example of fluoridizing phenol (b) comprises Pentafluorophenol, 3,5-difluorophenol, 3,4,5-trifluoromethyl phenol and 2,4,6-trifluoromethyl phenol.In addition, fluoridizing phenol can be separately or use as two or more mixtures, when using described mixture, preferably uses at least a phenol of fluoridizing that has on the phenyl ring in five hydrogen atoms structure that four or hydrogen atom still less replace by fluorine atom respectively.
As the inorganic particulate carrier of component (d) silica gel preferably.
Mentioned component (a) and (b) and (c) amount are not particularly limited, and when the mol ratio (a) of these component usage quantitys: (b): be 1 (c): x: during y, preferred x and y satisfy following formula:
|2-x-2y|≤1
In the above-mentioned formula, x represents to be preferably 0.01～1.99 numerical value, and more preferably 0.10～1.80, further preferred 0.20～1.50, most preferably 0.30～1.00.
About the usage quantity based on (d) of (a), derived from (a) be included in by (a) and (d) contact and the amount of zinc atom in the particulate that obtains is preferably 0.1mmol or more, more preferably 0.5～20mmol is with regard to the mole number of the zinc atom in being included in 1g gained particle.About the amount based on (e) of (d), every relatively g (d), amount (e) is preferably 0.1mmol or more, more preferably 0.5～20mmol.
By the metal such as the metallocene (B) of the bridged group structure connected to one another of alkylidene group or silicylene, the metal of the periodic table of elements the 4th family is preferred, more preferably zirconium and hafnium as two parts that wherein have cyclopentadienyl skeleton.
In addition, the example with part of cyclopentadienyl skeleton preferably includes indenyl, methyl indenyl, methyl cyclopentadienyl and dimethyl cyclopentadienyl, and the example of bridged group preferably includes vinyl, dimethylated methylene base and dimethylated methylene silylation.In addition, two groups of residue that are bonded on the metal for example preferably include phenoxy group or alkoxyl group.
As metallocene (B), ethylenebis (1-indenyl) zirconium diphenyl oxide compound preferably exemplifies.
Organo-aluminium compound (C) is triisobutyl aluminium or tri-n-octylaluminium preferably.
The usage quantity of metallocene (B) preferably every g promotor carrier (A) is 5 * 10
-6～5 * 10
-4Mol.With regard to aluminium atom (Al) at the mole number in the organo-aluminium compound (C) and atoms metal (M) with regard to the ratio (Al/M) of the mole number in the metallocene (B), the amount of organo-aluminium compound (C) preferably 1～2000.
By making component (A), (B) and (C) in the above-mentioned polymerizing catalyst of contact preparation, if desired, can contacting electron donor(ED) (D) in addition.Electron donor(ED) (D) is triethylamine or tri-n-octyl amine preferably.
Consider that molecular weight distribution broadens and the film transparency is improved, preferably use electron donor(ED) (D), and usage quantity (D) preferably relatively in the organo-aluminium compound (C) every mole of Al atom be 0.1mol% or more, more preferably 1mol% or more.On the other hand, consider the raising of polymerization activity, this measures preferably 10mol% or still less, more preferably 5mol% or still less.
Production method as ethene-alpha-olefin copolymer, preferred prepolymerized solid component copolymerization of ethylene and the alpha-olefin that obtains by the polymerization small amounts of olefins that use, described prepolymerized solid component is for example by using promotor carrier, metallocene and other cocatalyst component (for example alkylating reagent, as organo-aluminium compound) to obtain as catalyst component or catalyzer prepolymerization alkene.
Be used for prepolymerized alkene example and comprise ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene, 4-methyl-1-pentene, cyclopentenes and tetrahydrobenzene, and they can use separately, or two or more are used in combination.The content of prepolymerized polymkeric substance is 0.1～500g with respect to the ingredient of solid catalyst of every 1g normally in the prepolymerized solid component, preferred 1～200g.
As prepolymerization method, can use continuous polymerization method and batchwise polymerization method, for example can enumerate intermittently slurry polymerization, continuous slurry polymerization and continuous gas-phase polymerization.
As such as promotor carrier, metallocene and other cocatalyst component (alkylating reagent for example, as organo-aluminium compound) pack into the loading method of aggregation container of catalyst component, the loading method under conditions such as anhydrous and rare gas element such as nitrogen or argon gas, hydrogen, ethene normally, or with dissolution with solvents, dispersion or the solution after diluting each component or the slurry form loading method that adds each component.
In addition, in prepolymerization, as pack into the loading method of aggregation container of catalyst component, each component of preferably packing into is in order to handle the method that product forms pre-polymerized catalyst by handling the contact that the product of promotor carrier prepares with other promotor family branch contact position reason with the metallocene contact, the following method that exemplifies for example: (1) after aggregation container that promotor carrier and metallocene are packed into, other component packed into method of container, (2) will be by the aggregation container of packing into the contact processing product of metallocenes contact processing promotor carrier acquisition, subsequently to the method for other component of wherein packing into, (3) will handle pack into method in the aggregation container that other component packed into of product by handle contact that the promotor carrier obtains with metallocenes contact, (4) will handle contact that the product of promotor carrier prepares with the metallocene contact and handle method that the pre-polymerized catalyst of product formation packs into etc. by handling with other cocatalyst component contact.
The promotor carrier is handled with contacting of metallocene and is preferably carried out in inert solvent such as aliphatic hydrocrbon (for example butane, pentane, hexane, octane) and aromatic hydrocarbon (for example benzene, toluene) etc., consider the enhancing of optical property, preferably 50～100 ℃ of contact treatment temps.
The prepolymerization temperature is usually less than prepolymerized melting point polymer, and preferred 0～100 ℃, more preferably 10～70 ℃.
When carrying out prepolymerization by slurry polymerization, the specific examples of the solvent of use comprises aliphatic hydrocarbon such as propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, hexanaphthene, heptane, octane and decane; With aromatic hydrocarbon such as benzene, toluene and dimethylbenzene, they can use separately, or two or more are used in combination.
Production method as ethene-alpha-olefin copolymer, it is preferred following the continuous polymerization method that forms the ethene-alpha-olefin copolymer particle, for example, continuous gas-phase polymerization method, method for continuous slurry polymerization and continuous bulk polymerization process are preferred, wherein, the continuous gas-phase polymerization method is most preferred.The gas-phase polymerization apparatus that uses contains the fluidised bed polymerisation container usually, preferably contain the gas-phase polymerization apparatus with expansion section s, and agitating vane can be installed in this container.
Supply method as prepolymerized solid catalyst component in following the successive polymerization container that forms the ethene-alpha-olefin copolymer particle, usually can be the method for feed under conditions such as anhydrous and rare gas element such as nitrogen or argon gas, hydrogen, ethene, or after each component is with dissolution with solvents, dispersion or dilution, supply with the method for each component with solution or slurry form.
Follow the polymerization temperature that forms the ethene-alpha-olefin copolymer particle to be usually less than the temperature of fusion of multipolymer, preferred 0～150 ℃, more preferably 30～100 ℃.
In addition, consider the improvement of ethene-alpha-olefin copolymer film transparency of the present invention, temperature preferably is lower than 90 ℃, and preferred 70～87 ℃ particularly, more preferably 70～85 ℃, further preferred 72～80 ℃.In addition, for the purpose of the fluidity of molten of the ethene-alpha-olefin copolymer of controlling production, hydrogen can be used as molecular weight regulator and adds.In addition, the rare gas element in the monomer mixed gas can coexist.When using prepolymerized solid catalyst, can suitably use cocatalyst component such as organo-aluminium compound.
In the production of ethene-alpha-olefin copolymer of the present invention, preferably comprise the method for mediating the ethene-alpha-olefin copolymer step, this ethene-alpha-olefin copolymer obtains in order to the lower device polymerization: (1) increases flow and mediates die head, for example, by people such as Utracki exploitation and be disclosed in U.S.Pat.5,451, die head in 106, (2) be equipped with the counter-rotating twin screw forcing machine, this counter-rotating twin screw has toothed gear pump, the maintaining part that preferably has between screw rod and die head is graded.
Ethene-alpha-olefin copolymer of the present invention can be chosen wantonly and contain known additives.The example of additive comprises antioxidant, weather resisting agent, lubricant, anti-hard caking agent, static inhibitor, demisting agent, not sagging agent, pigment, filler etc.
Film of the present invention can be by known molding methods production, and extrusion process for example is as blown film molding methods or T-die head film molding methods.As molding methods, preferably use extrusion molding.Consider the raising of weathering resistance, film of the present invention is molding under 180 ℃ of temperature or lower temperature preferably, more preferably 170 ℃ or lower.On the other hand, consider to reduce and extrude load, preferably molding under 130 ℃ or higher temperature.
As the molding methods condition of film of the present invention, consider the raising of film weathering resistance, extrusion capacity, die lip area and the die lip wavelength width of a slit of preferably drawing speed, resin satisfy following formula (2):
20＜V＜((M/A)×W)＜150 (2)
V: draw speed (m/min)
M: the resin extruded amount (kg/hr) of die lip
A: die lip area (mm
2)
W: die lip wavelength width of a slit (mm)
The vinyl polymer that constitutes film is the polymkeric substance that contains a large amount of following molecular structures, molecular chain ruptures by the light that is exposed to as UV easily in the polymkeric substance high molecular weight component in described molecular structure, and after 250 hours carbon arc lamps are handled molecular weight distribution ([Mw/Mn] a) satisfies following formula (1):
0.6＜[Mw/Mn]
a/[Mw/Mn]
b＜1.2
[Mw/Mn]
a: the molecular weight distribution of film after 250 hours carbon arc lamps are handled
[Mw/Mn]
b: the molecular weight distribution of film before this is handled
When the vinyl polymer that constitutes film contains the molecular structure that molecular chain ruptures by the light that is exposed to as UV easily in a large number, in the lower-molecular-weight component of polymkeric substance, molecular weight distribution ([Mw/Mn] after 250 hours carbon arc lamps are handled
a) become greater than the molecular weight distribution ([Mw/Mn] before this processing
b), therefore, do not satisfy the relation of above-mentioned formula (1).
The carbon arc lamp of film is handled at 50V sparking voltage, 60A discharging current, 255Wm
2(300-700nm) yield of radiation, 83 ℃ of blackboard temperatures, and the condition of 18 minutes water sprays and the water spray circulation of not spraying water in 102 minutes under carried out 250 hours.In addition, the molecular weight distribution of film (Mw/Mn) is by gpc measurement weight-average molecular weight (Mw) and number-average molecular weight (Mn) and definite divided by the value of Mn with Mw.For example, as the measuring condition of GPC, what can enumerate is the condition of describing in the paragraph about the vinyl polymer molecular weight.
In addition, consider the raising weathering resistance, film of the present invention preferably satisfy following formula (1) ', more preferably satisfy formula (1) ".
[Mw/Mn]
a/[Mw/Mn]
b＜1.0 (1)′
[Mw/Mn]
a/[Mw/Mn]
b＜0.9 (1)″
In addition, consider the raising weathering resistance, film of the present invention preferably satisfies following formula (1) " ':
0.7＜[Mw/Mn]
a/[MW/Mn]
b (1)″′
Because film of the present invention is excellent aspect weathering resistance, so it is fit to the long-term film that acts on plant-growth places such as covering greenhouse production, shed cultivation of using.
Embodiment
The present invention will describe in detail by the following examples and Comparative Examples.
Physicals in embodiment and the Comparative Examples is measured by following method:
[physicals of polymkeric substance and structure]
(1) melt flow rate (MFR) (MFR)
Under 190 ℃ and 21.18N load-up condition, measure by the A-method according to JIS K7210-1995.
(2) melt flow rate (MFR) is than (MFRR)
Melt flow rate (MFR) is the value that obtains divided by the melt flow rate value of measuring under 21.18N load by the melt flow rate value of measuring under 190 ℃, 211.82N load according to JIS K7210-1995 than (MFRR).For the measurement of above-mentioned melt flow rate (MFR), use to add 1000wt-ppm antioxidant (Irganox in advance
1076, Ciba Specialty Chemicals Ltd. manufacturing) polymkeric substance.
(3) density (unit: kg/m
3)
After according to JIS K6760-1995 annealing, measure the density of multipolymer according to the A method among the JIS K7112-1980.
(4) fluid-activated can (Ea, unit: kJ/mol)
Melt complex viscosity and radian frequency 130 ℃, 150 ℃, 170 ℃ and 190 ℃ use viscoelasticity measurement instrument (Rheometrics Mechanical Spectrometer RMS-800 under following condition, made by Rheometrics Limited) measure preparation melt complex viscosity-radian frequency curve.According to the curve that obtains, use computer software Rhios V.4.4.4 (by Rheometrics, Limited makes) makes melt complex viscosity-radian frequency master curve of 190 ℃, and definite activation energy (Ea).
＜measuring condition 〉
Geometry: parallel plate
Board diameter: 25mm
Distance between plates: 1.5～2mm
Tension force: 5%
Radian frequency: 0.1～100rad/s
Measure atmosphere: nitrogen
(5) molecular weight distribution (Mw/Mn)
Use gel permeation chromatography (GPC) at following (i)～(viii) measure weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the condition, and definite Mw/Mn.
Baseline in the color atlas is set at straight line, and the point that wherein has in the maintenance level zone of the retention time of comparing enough weak points with the sample eluting peak that occurs links to each other with point in having the zone, stabilize water plane of comparing sufficiently long retention time with observed solvent eluting peak.
(i) instrument: Waters 150C (Water limited manufacturing)
(ii) separator column: TOSOH TSKgelGMH6-HT
(iii) measure temperature: 140 ℃
(iv) carrier: orthodichlorobenzene
(v) flow: 1.0mL/min
(vi) injection rate: 500 μ L
(vii) detector: differential refraction
(vlii) reference material of molecular weight: polystyrene standard
(6) the flex point number on the melting curve and maximum fusing point (Tm, unit: ℃)
Vinyl polymer obtains the thick thin slice of 100 μ m after 5 minutes, being cooled to 30 ℃ with chilling press with 150 ℃ of thermocompressor compactings under the 10MPa pressure, then this thin slice is cut into the sample of about 10mg.Sample is encapsulated in the aluminium dish.
Next, enclose aluminium dish differential scanning calorimeter (the differential scanning calorimeter DSC-7 type of sample, Perkin Elmer Co.Ltd. makes) carry out the measurement of melting curve according to following program: (1) maintain 150 ℃ 5 minutes, (2) speed with 5 ℃/min is cooled to 20 ℃ from 150 ℃, (3) maintain again 20 ℃ 2 minutes, (4) further be heated to 150 ℃ from 20 ℃, obtain curve from step (4).According to the melting curve that obtains, determine the temperature at melting peak place and be present in 25 ℃ of flex point numbers in fusion end points (this point is melting curve in the temperature that high temperature one side the is got back to baseline) scope that described melting peak has at 25 ℃ and arrives observed climax in the melted ends point range.
[membrane structure]
The ratio ([Mw/Mn] of the molecular weight distribution before the molecular weight distribution of (7) 250 hours carbon arc lamp exposure-processed caudacorias and this are handled
a/ [Mw/Mn]
b)
Measure down the molecular weight distribution of film after 250 hours carbon arc lamp exposure-processed [(Mw/Mn) in above-mentioned condition (5)
a] and the molecular weight distribution of film before handling [(Mw/Mn)
b], and by calculating definite [Mw/Mn]
a/ [Mw/Mn]
b
(treatment condition)
Instrument: Sunshine Weather Meter (SUGA TEST INSTRUMENTS CO., LTD makes)
Light source: daylight carbon arc lamp
Sparking voltage: 50V
Discharging current: 60A
Yield of radiation: 255Wm
2(300-700nm)
Blackboard temperature: 83 ℃
Water spray circulation: sprayed water 18 minutes and do not spray water 102 minutes
Treatment time: 250 hours
[film properties]
(8) the fracture stretching can ratio (unit: %)
Film is according to the shape punching preparation test piece of JIS Z1702 regulation.Some of them stand aforesaid carbon arc lamp to be handled, except the treatment time is 250 hours and 150 hours.Make processing sample and untreated sample afterwards of such acquisition stand tension test respectively, the clamp distance of tensile testing machine is that 80mm and draw speed are 500mm/min, from the stress-stretching distance curve that obtains respectively, determine that the integrated value of stress-stretching distance curve is as fracture stretching energy.And every kind of sample has five test pieces to stand tension test to determine fracture stretching energy, five values of average measurement.
E (150) and E as 150 hours stretching energy that rupture after the carbon arc lamp exposure-processed
0Ratio [E (150)/E
0] and as fracture after 250 hours carbon arc lamp exposure-processed stretch can E (250) and E
0Ratio [E (250)/E
0] fracture of each free untreated samples stretches can (E
0), the fracture of handling the back sample in the 150 hours fracture of can (E (150)) and handling the back sample in 250 hours that stretches stretches and can (E (250)) calculate acquisition.As E (150)/E
0And E (250)/E
0When big, the having excellent weather resistance of film.
(9) tensile fracture elongation rate ratio (unit: %)
In above-mentioned (8), in the tension test of mensuration fracture stretching energy ratio, the distance between the graticule when test piece is broken is measured in test piece and the test piece of daylight carbon arc lamp processing after 200 hours that no daylight carbon arc lamp is handled respectively.Distance (L from the coupons that is untreated
0) and stand the distance (L that the daylight carbon arc lamp is handled the coupons after 200 hours
200), calculate L
200With L
0Ratio [L
200/ L
0], define this than being " tensile fracture elongation rate ".
When the tensile fracture elongation rate was big, the weathering resistance of film was more excellent.
[mouldability of film]
(10) resin pressure (unit: MPa)
[Placo.Ltd. makes when the thick blown film of 100 μ m is used the blown film forming mill under 170 ℃ of molding temperatures, 5.5kg/hr extrusion capacity, 200mm frost line distance (FLD) and 1.8 blow-up ratio conditions, perfect thread type single screw extrusion machine (screw diameter 30mm Φ, L/D=28), die head (die diameter 50mm Φ, lip slit 0.8mm), double slit ventilates] when forming, measure the resin pressure of forcing machine.
When resin pressure was low, formability was more excellent.
Embodiment 1
(1) preparation of promotor carrier
With nitrogen purging the reactor of agitator is housed, (Sylopol 948, and by Devison, Ltd. makes at 300 ℃ of heat treated silicas to the 0.36kg that wherein packs under nitrogen gas stream; 50% volume average particle size=59 μ m; Void content=1.68ml/g; Specific surface area=313m
2/ g) and the toluene of 3.5l, stir the mixture of gained then.Mixture is cooled to 5 ℃, and then with 1,1,1,3,3 of 0.15l, the toluene mixing solutions of 3-hexamethyldisilazane and 0.2l was added dropwise to wherein in 30 minutes, remained on 5 ℃ simultaneously.After being added dropwise to complete, stirred the mixture 1 hour at 5 ℃, stirred 3 hours and filtered at 95 ℃ after being heated to 95 ℃ then.The solid of Huo Deing is used the 2l toluene wash six times at every turn like this.Afterwards, the toluene that adds 2l obtains slurry, then with the mixture standing over night.
Pack in the slurry of above-mentioned acquisition hexane solution (the zinc ethyl concentration: 2mol/l), stir then of zinc ethyl of 0.27l.After this, mixture is cooled to 5 ℃, the mixing solutions with 0.05kg Pentafluorophenol and 0.09l toluene was added dropwise to wherein in 60 minutes then, remained on 5 ℃ simultaneously.After being added dropwise to complete, mixture stirred 1 hour at 5 ℃, be heated to 40 ℃ then after, stirred 1 hour at 40 ℃.After being cooled to 5 ℃ then, in 1.5 hours, drip the H of 7g
2O remains on 5 ℃ simultaneously.After being added dropwise to complete, mixture stirred 1.5 hours at 5 ℃, further stirred 2 hours at 55 ℃ after being heated to 55 ℃.Then, behind the cool to room temperature, with hexane solution (the zinc ethyl concentration of the zinc ethyl of 0.63l; 2mol/l) join in this product.After being cooled to 5 ℃, with 3,4 of 94g, the toluene mixing solutions of 5-trifluoromethyl phenol and 0.2l was added dropwise to wherein in 60 minutes, and keeping the inside reactor temperature simultaneously is 5 ℃.After being added dropwise to complete, the mixture of gained stirred 1 hour at 5 ℃, further was heated to 40 ℃, stirred 1 hour at 40 ℃.Thereafter, the mixture with gained is cooled to be added dropwise to the H of 17g after 5 ℃ in 1.5 hours
2O, the temperature that keeps inside reactor simultaneously is 5 ℃.After being added dropwise to complete, the mixture of gained stirred 1.5 hours at 5 ℃, be heated to 40 ℃ after, stirred 2 hours at 40 ℃, further stirred 2 hours at 80 ℃ after being heated to 80 ℃.
, this product left standstill cause the precipitation of solid ingredient, when observing the interface of precipitated solid component layers and upper strata slurry part, remove the slurry part on upper strata, then the remaining liq component is removed by strainer thereafter.
In addition, carry out following operation:
" the toluene that adds 3L.With the mixture heating up to 95 of gained ℃, then at 95 ℃ stir 2 hour thereafter.Mixture is left standstill to cause the precipitation of solid ingredient, when observing the interface of precipitated solid component layers and upper strata slurry part, remove the slurry part on upper strata, the remaining liq component is removed by strainer then.”
Next, carry out the operation of similar aforesaid operations, carry out four times at 95 ℃ of each toluene of 3l that use, at room temperature use the hexane of 3l to carry out then at every turn twice.After this operation, the solid of generation is drying at room temperature 1 hour under reduced pressure, obtains solid ingredient (being called " promotor carrier (a) ").
(2) preparation of pre-polymerized catalyst components
In advance with the autoclave that agitator is housed of nitrogen purging 210L volume capacity, under normal temperature and normal pressure, pack in this autoclave butane of 80l and the hydrogen of 2l, pack into then racemize-ethylenebis (1-indenyl) zirconium diphenyl oxide compound of 107.5mmol, with the mixture heating up to 50 of gained ℃, stirred then 2 hours.Next, autoclave is cooled to 30 ℃.After system is stable, to depress corresponding to the gas phase of 0.06MPa ethene is packed in this autoclave, and the above-mentioned promotor carrier (a) of the 0.7kg that packs into, the triisobutyl aluminium of the 158mmol that then packs into is with initiated polymerization.
The ethene of 0.7kg/hr of packing into continuously at the same time and the hydrogen of 4.2l/hr (volume under the normal temperature and pressure) are through after 30 minutes, along with temperature is elevated to 50 ℃, the ethene of 3.5kg/hr of packing into continuously and the hydrogen of 2l/hr (volume under the normal temperature and pressure) carry out 4 hours polyreaction thus altogether.After prepolymerization is finished, ethene, butane, hydrogen etc. are purged, the vacuum-drying at room temperature of remaining solid obtains pre-polymerized catalyst components, wherein the above-mentioned promotor carrier of every 1g (a) prepolymerization the ethene of 15.8g.
(3) production of vinyl polymer
Use the above pre-polymerized catalyst components that obtains, in successive type fluidized bed gas-phase polymerization device, carry out the copolymerization of ethene and 1-hexene, obtain ethene-1-hexene copolymer powder.
Polymerizing condition comprises the mol ratio 1.536 of 85 ℃ of polymerization temperatures, polymerization pressure 2MPa, hydrogen and ethene and the mol ratio 1.32 of 1-hexene and ethene and 1-hexene total amount, and in polymerization process, ethene, 1-hexene and hydrogen charging continuously are constant to keep gas composition.In addition, above-mentioned pre-polymerized catalyst components and triisobutyl aluminium continuously charging in order to keep the constant total powder weight of 80kg in the fluidized-bed.The average polymerization time is 4 hours.
The ethene of Huo Deing-1-hexene copolymer powder and the antioxidant of 750ppm (Sumitomo Chemical Co., Ltd. manufacturing, trade(brand)name: Sumilizer so by weight
GP) blend, use forcing machine (Kobe Steel Ltd. make LCM50) granulation under the feeding rate of 50kg/hr, 450rpm screw speed, 50% lock hole aperture, 0.1MPa negative pressure and 200～230 ℃ of resin temperature conditions then, obtain ethene-1-hexene copolymer.
(4) preparation of vinyl polymer film
Ethene-1-hexene copolymer blown film mould machine [Placo, Ltd. make, perfect thread type single screw extrusion machine (screw diameter 30mm Φ, L/D=28), die head (die diameter 50mm Φ, lip slit 0.8mm) and double slit ventilate] at 170 ℃ of molding temperatures, extrusion capacity 5.5kg/hr, frost line distance (FLD) 200mm, blow-up ratio 1.8 with draw under the condition of moulding of speed 3.84m/min and be molded as the thick film of 100 μ m.
The assessment result of gained ethene-1-hexene copolymer film sees Table 1.
Embodiment 2
(1) preparation of vinyl polymer film
The pre-polymerized catalyst components that uses the continuous fluid bed bioreactor and obtain in (2) carries out the copolymerization of ethene, 1-butylene and 1-hexene.
With with embodiment 1 in identical mode prepare the pre-polymerized catalyst components of embodiment 1, except the mol ratio of hydrogen and ethene changes into 2.2, the comonomer of packing into is changed into 1-butylene and 1-hexene, the mol ratio of 1-butylene and 1-hexene and ethene, 1-butylene and 1-hexene total amount is adjusted to 2.6 and 1.0 respectively, like this multipolymer of Huo Deing use with embodiment 1 in identical mode granulation, obtain ethene-1-butylene-1-hexene copolymer.
(2) preparation of vinyl polymer film
Ethene-1-butylene-1-hexene copolymer that above-mentioned (1) is obtained use with embodiment 1 (4) in identical mode be molded as the blown film of 100 μ m.The assessment result of gained film sees Table 1.
Comparative Examples 1
Linear low density polyethylene [by Sumitomo Chemical, Co., Ltd. makes, trade(brand)name: Sumikathene
-L FS150 (producing with Ziegler-type catalyst)] usefulness blown film mould machine [Placo, Ltd. make, perfect thread type single screw extrusion machine (screw diameter 30mm Φ, L/D=28), die head (die diameter 125mm Φ, lip slit 2.0mm) and double slit ventilate] at 200 ℃ of molding temperatures, extrusion capacity 25.0kg/hr, frost line distance (FLD) 200mm, blow-up ratio 1.8 and draw under the condition of moulding of speed 6m/min and be molded as the thick film of 100 μ m.The assessment result of gained film sees Table 1.
Comparative Examples 2
Linear low density polyethylene [by Sumitomo Chemical, Co., Ltd. makes, trade(brand)name: Sumikathene
-E FV201 (producing with metallocene-type catalyst)] use with Comparative Examples 1 in identical mode be molded as the thick film of 100 μ m.The assessment result of gained film sees Table 1.
Comparative Examples 3
Linear low density polyethylene (by Dow Chemical, Co., Ltd. makes, trade(brand)name: Dowlex
-2045G) use with Comparative Examples 1 in identical mode be molded as the thick film of 100 μ m.The assessment result of gained film sees Table 1.
Comparative Examples 4
(Ltd. makes hp-ldpe, trade(brand)name: Sumikathene for Sumitomo Chemical, Co.
F208-0) use with Comparative Examples 1 (4) in identical mode be molded as the film of 100 μ m.The assessment result of gained film sees Table 1.
Comparative Examples 5
The ethene that obtains among the embodiment 1-1-hexene copolymer blown film shaper [Placo, Ltd. make, perfect thread type single screw extrusion machine (screw diameter 30mm Φ, L/D=28), die head (die diameter 125mm Φ, lip slit 2.0mm) and double slit ventilate] at 200 ℃ of molding temperatures, extrusion capacity 25.0kg/hr, frost line distance (FLD) 200mm, blow-up ratio 1.8 with draw under the condition of moulding of speed 12m/min and be molded as the thick film of 50 μ m.The assessment result of gained film sees Table 1.
Comparative Examples 6
(1) preparation of promotor carrier
With nitrogen purging four neck flasks, to the toluene of 0.2kg heat treated silica (Sylopol 948, and by Devison, Ltd. makes) and the 1.2l under 300 ℃ of nitrogen gas stream that wherein pack into.The mixture of gained is cooled to 5 ℃, dripped 1,1,1,3,3 of 84.4ml then in 25 minutes, the mixing solutions of 3-hexamethyldisilazane and 115ml toluene remains on 5 ℃ simultaneously.After being added dropwise to complete, mixture stirred 1 hour at 5 ℃, be heated to 95 ℃ after, stirred 3 hours at 95 ℃, filter.The solid of Huo Deing is used the toluene wash four times of 1.2l at every turn like this, and the toluene that after this adds 1.2l obtains slurry, then with the mixture standing over night.
Pack in the slurry of above-mentioned acquisition hexane solution (the zinc ethyl concentration: 2mol/l), mixture is cooled to 5 ℃ then of zinc ethyl of 0.55l.Next, the mixing solutions of 105g Pentafluorophenol and 173ml toluene was added dropwise to wherein in 65 minutes, remains on 5 ℃ simultaneously.After being added dropwise to complete, mixture stirred 1 hour at 5 ℃, was heated to 40 ℃ then, stirred 1 hour at 40 ℃.Then, be cooled in 1.5 hours, be added dropwise to the H of 14.9g after 5 ℃
2O, the temperature of flask remains on 5 ℃ simultaneously.After being added dropwise to complete, mixture stirred 1.5 hours at 5 ℃, further stirred 2 hours at 40 ℃ after being heated to 40 ℃.
After this with the product standing over night.Next, be heated to 80 ℃, stirred 2 hours at 80 ℃, it is left standstill to cause the precipitation of solid ingredient, when observing the interface of precipitated solid component layers and upper strata slurry part, remove the slurry part on upper strata, the remaining liq component is removed by strainer then, add the toluene of 1.7l in the solid ingredient, stirred 2 hours at 95 ℃.
After this, carry out following operation:
" the toluene that adds 1.7l.With the mixture heating up to 95 of gained ℃, at 95 ℃ stir 2 hour thereafter.Mixture is left standstill to cause the precipitation of solid ingredient, when observing the interface of precipitated solid component layers and upper strata slurry part, remove the slurry part on upper strata, then the remaining liq component is removed by strainer.”
Next, carry out the operation of similar aforesaid operations, use the toluene of 1.7l to carry out three times at 95 ℃, use the hexane of 1.7l at room temperature to carry out twice then.After this operation, the solid of gained is drying at room temperature 3 hours under reduced pressure, obtains solid ingredient (being called " promotor carrier (b) ").
(2) preparation of pre-polymerized catalyst components
In advance with the autoclave that agitator is housed of nitrogen purging 210L volume capacity, the 80l that packs in this autoclave under normal temperature and normal pressure contains the butane of 2.5mmol/l concentration triisobutyl aluminium, the 1-butylene of 0.05l and the hydrogen of 11l, autoclave is heated to 23 ℃ then.Next, ethene is with in this autoclave of packing into corresponding to the amount of the gaseous pressure of 0.2MPa.After system is stable, see (1-indenyl) zirconium diphenyl oxide compound to racemize-ethylidene of the triisobutyl aluminium that wherein adds 10mmol and 70mmol, add the above-mentioned promotor carrier (b) of 0.63kg subsequently with initiated polymerization, and prepolymerization was carried out 4 hours.In pre-polymerization process, ethene and hydrogen are fed in the autoclave continuously, autoclave temp is adjusted to 50 ℃.
After prepolymerization is finished, ethene, butylene, hydrogen etc. are purged.The vacuum-drying at room temperature of remaining solid obtains pre-polymerized catalyst components, wherein the above-mentioned promotor carrier of every 1g (b) prepolymerization the ethene of 14g.
(3) production of vinyl polymer
Use the above pre-polymerized catalyst components that obtains, in successive type fluidized bed gas-phase polymerization device, carry out the copolymerization of ethene and 1-hexene, obtain ethene-1-hexene copolymer powder.
Polymerizing condition comprises the mol ratio 0.573 of 75 ℃ of polymerization temperatures, polymerization pressure 2MPa, hydrogen and ethene and the mol ratio 1.02 of 1-hexene and ethene and 1-hexene total amount, and in polymerization process, ethene, 1-hexene and hydrogen charging continuously are constant to keep gas composition.In addition, above-mentioned pre-polymerized catalyst components and triisobutyl aluminium continuously charging in order to keep the constant total powder weight of 80kg in the fluidized-bed.The average polymerization time is 4 hours.
The ethene of Huo Deing-1-hexene copolymer powder and the antioxidant of 750ppm (Sumitomo Chemical Co., Ltd. manufacturing, trade(brand)name: Sumilizer so by weight
GP) blend, use forcing machine (Kobe Steel Ltd. make LCM50) granulation under the feeding rate of 50kg/hr, 450rpm screw speed, 50% lock hole aperture, 0.1MPa negative pressure and 200～230 ℃ of resin temperature conditions then, obtain ethene-1-hexene copolymer.
(4) preparation of vinyl polymer film
The ethene of above-mentioned acquisition-1-hexene copolymer uses the mode identical with Comparative Examples 1 to be molded as the thick film of 100 μ m.The assessment result of gained ethene-1-hexene copolymer film sees Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 | Comparative Examples 6 | |
| The multipolymer physical properties | ||||||||
| MFR(g/10min) | 0.45 | 0.9 | 1.1 | 2.3 | 0.99 | 1.54 | 0.45 | 0.52 |
| MFRR | 120.9 | 88.0 | 22.7 | 24.7 | 29.4 | 50.2 | 120.9 | 134.3 |
| Density (kg/m 3) | 920.4 | 919.1 | 921.0 | 916.0 | 921.0 | 922.0 | 920.4 | 921.0 |
| Ea(kJ/mol) | 71.6 | 68.8 | 28.9 | 35.8 | 32.3 | 62.5 | 71.6 | 73.4 |
| Mw/Mn | 9.0 | 8.8 | - | - | - | - | 9.0 | 8.8 |
| Maximum thawing peak temperature (℃) | 111.5 | 108.3 | 124.1 | 113.3 | 124.9 | 111.5 | 111.5 | 104.5 |
| The flex point number | 2 | 2 | 4 | 7 | 7 | 2 | 2 | 4 |
| The film processing conditions | ||||||||
| D/((L/A)·W) | 111 | 111 | 95 | 95 | 95 | 95 | 191 | 95 |
| Membrane structure | ||||||||
| [Mw/Mn]b | 9.0 | 8.6 | 4.2 | 3.6 | 3.9 | 4.0 | 9.6 | 8.8 |
| [Mw/Mn]a/[Mw/Mn]b | 0.8 | 0.825 | 1.47 | 1.44 | 1.41 | 1.98 | 0.52 | 0.48 |
| Film properties | ||||||||
| E(150)/E0 | 0.905 | 0.696 | 0.549 | 0.691 | 0.715 | 0.400 | 0.82 | 0.77 |
| E(250)/E0 | 0.159 | 0.187 | 0.022 | 0.065 | 0.113 | 0.076 | 0.025 | 0.023 |
| Tensile fracture elongation rate (%) | 53 | 51 | 8 | 39 | 34 | 17 | 34 | 23 |
| The mouldability of film | ||||||||
| Resin pressure (MPa) | 31 | 26 | - | - | - | 36 | - | - |
Claims (2)
1. film that obtains by the molding vinyl polymer, this vinyl polymer have based on the monomeric unit of ethene with based on the monomeric unit of the alpha-olefin with 3～20 carbon atoms, the molecular weight distribution of wherein said film [Mw/Mn]
bWith the molecular weight distribution [Mw/Mn] of described film through 250 hours daylight carbon arc lamp exposure-processed caudacorias
aSatisfy the relation of following formula (1):
0.7<[Mw/Mn]
a/[Mw/Mn]
b<1.0 (1)
Wherein the implementation condition of this 250 hours daylight carbon arc lamp exposure-processed is the 255Wm at 50V sparking voltage, 60A discharging current, 300-700nm
2Yield of radiation, 83 ° of C of blackboard temperature, and the condition of 18 minutes water sprays and the water spray circulation of not spraying water in 102 minutes under carried out 250 hours;
The therein ethylene based polyalcohol has the melt flow rate (MFR) of 0.01～10g/10min, and wherein this melt flow rate (MFR) is to measure down at 190 ° of C load 21.18N (2.16Kg) according to the A-method among the JISK7210-1995; With
The therein ethylene based polyalcohol has 50kJ/mol or bigger fluid-activated energy, and wherein this fluid-activated can be by the shift factor (a in the master curve preparation according to the Arrhenius equation
T) numerical value that calculates.
2. method of producing film, it is included in and satisfies following all conditions (i)～(molding vinyl polymer resins film forming under the condition v), this vinyl polymer resins has based on the monomeric unit of ethene with based on the monomeric unit of the alpha-olefin with 3～20 carbon atoms, draws amount M (kg/hr), die lip area A (mm that speed V (m/min), resin extrude from die lip under the described conditions
2) and die lip width W (mm) satisfy following formula (2):
(i) melt flow rate (MFR) is 0.01～10g/10min, and this melt flow rate (MFR) is to measure down at 190 ° of C load 21.18N (2.16Kg) according to the A-method among the JISK7210-1995,
(ii) density (d) is 890～970kg/m
3,
(iii) fluid-activated can (Ea) be 50kJ/mol or bigger, and wherein this fluid-activated can be by the shift factor (a in the master curve preparation according to the Arrhenius equation
T) numerical value that calculates,
(iv) molecular weight distribution (Mw/Mn) be 3～25 and
(it is 3 or still less that flex point number on the melting curve between the temperature is finished in 25 ° of C that v) obtain by dsc and fusion,
20<V/((M/A)×W)<150 (2)。
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| JP2007081169 | 2007-03-27 | ||
| JP2007081169A JP4935454B2 (en) | 2006-07-03 | 2007-03-27 | Film and film manufacturing method |
| JP2007-081169 | 2007-03-27 |
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| CN1392190A (en) * | 2001-04-23 | 2003-01-22 | 三井化学株式会社 | Process for preparing ethylene polymer composition, ethylene polymer composition particles and film made from said particles |
| JP3672394B2 (en) * | 1996-11-06 | 2005-07-20 | 出光興産株式会社 | Ethylene copolymer and film comprising the same |
| CN1644351A (en) * | 2003-09-26 | 2005-07-27 | 住友化学工业株式会社 | Method for producing ethylene polymer film and the film |
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| CA2103401C (en) * | 1992-11-19 | 2002-12-17 | Mamoru Takahashi | Ethylene copolymer composition |
| JP2003105202A (en) * | 2001-09-27 | 2003-04-09 | Sekisui Chem Co Ltd | Weather-resistant resin composition |
| JP4815820B2 (en) * | 2004-03-30 | 2011-11-16 | 住友化学株式会社 | Laminating film and laminated film |
| JP4797486B2 (en) * | 2004-07-28 | 2011-10-19 | 住友化学株式会社 | Polyethylene resin composition, film and bag |
| JP2006137848A (en) * | 2004-11-12 | 2006-06-01 | Sumitomo Chemical Co Ltd | Inflation film |
| JP2006142685A (en) * | 2004-11-22 | 2006-06-08 | Sumitomo Chemical Co Ltd | Method of manufacturing inflation film |
| JP5493238B2 (en) * | 2005-09-30 | 2014-05-14 | 住友化学株式会社 | Ethylene-α-olefin copolymer and molded product |
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| JP3672394B2 (en) * | 1996-11-06 | 2005-07-20 | 出光興産株式会社 | Ethylene copolymer and film comprising the same |
| CN1392190A (en) * | 2001-04-23 | 2003-01-22 | 三井化学株式会社 | Process for preparing ethylene polymer composition, ethylene polymer composition particles and film made from said particles |
| CN1644351A (en) * | 2003-09-26 | 2005-07-27 | 住友化学工业株式会社 | Method for producing ethylene polymer film and the film |
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| CN101100524A (en) | 2008-01-09 |
| JP2008031418A (en) | 2008-02-14 |
| ES2322742B1 (en) | 2010-02-26 |
| JP4935454B2 (en) | 2012-05-23 |
| ES2322742A1 (en) | 2009-06-25 |
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