CN1226341C - Ethylene copolymer composition - Google Patents
Ethylene copolymer composition Download PDFInfo
- Publication number
- CN1226341C CN1226341C CNB021228094A CN02122809A CN1226341C CN 1226341 C CN1226341 C CN 1226341C CN B021228094 A CNB021228094 A CN B021228094A CN 02122809 A CN02122809 A CN 02122809A CN 1226341 C CN1226341 C CN 1226341C
- Authority
- CN
- China
- Prior art keywords
- mfr
- alpha
- ethylene
- olefin
- olefin copolymer
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 229920001038 ethylene copolymer Polymers 0.000 title claims abstract description 66
- 239000004711 α-olefin Substances 0.000 claims abstract description 212
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 202
- 239000005977 Ethylene Substances 0.000 claims abstract description 156
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 152
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 81
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000155 melt Substances 0.000 claims abstract description 21
- 229920001577 copolymer Polymers 0.000 claims abstract description 14
- 150000002736 metal compounds Chemical class 0.000 claims description 82
- 238000006116 polymerization reaction Methods 0.000 claims description 59
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 47
- 150000003624 transition metals Chemical class 0.000 claims description 46
- 150000001336 alkenes Chemical class 0.000 claims description 42
- 150000001875 compounds Chemical class 0.000 claims description 41
- 239000003446 ligand Substances 0.000 claims description 36
- 238000006555 catalytic reaction Methods 0.000 claims description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 32
- 239000003595 mist Substances 0.000 claims description 22
- 229910052723 transition metal Inorganic materials 0.000 claims description 14
- 238000010008 shearing Methods 0.000 claims description 12
- 238000001595 flow curve Methods 0.000 claims description 11
- 230000008698 shear stress Effects 0.000 claims description 11
- 238000000071 blow moulding Methods 0.000 claims description 10
- 230000002195 synergetic effect Effects 0.000 claims description 9
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
- -1 trialkylsilkl Chemical group 0.000 description 152
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 128
- 229910052726 zirconium Inorganic materials 0.000 description 126
- 239000000126 substance Substances 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 229910052782 aluminium Inorganic materials 0.000 description 51
- 238000002360 preparation method Methods 0.000 description 47
- 239000003054 catalyst Substances 0.000 description 42
- 238000000034 method Methods 0.000 description 41
- 235000010210 aluminium Nutrition 0.000 description 38
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 32
- 239000004411 aluminium Substances 0.000 description 31
- 125000000217 alkyl group Chemical group 0.000 description 30
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 27
- 239000011949 solid catalyst Substances 0.000 description 27
- 150000002899 organoaluminium compounds Chemical class 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 229910052799 carbon Inorganic materials 0.000 description 20
- 238000005660 chlorination reaction Methods 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000007789 gas Substances 0.000 description 16
- 101150116295 CAT2 gene Proteins 0.000 description 15
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 15
- 239000004215 Carbon black (E152) Substances 0.000 description 15
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 14
- 150000002430 hydrocarbons Chemical class 0.000 description 14
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 14
- 238000005259 measurement Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 12
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 12
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 12
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 12
- 125000005843 halogen group Chemical group 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000004104 aryloxy group Chemical group 0.000 description 10
- 239000000725 suspension Substances 0.000 description 9
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 230000000452 restraining effect Effects 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 7
- 238000005469 granulation Methods 0.000 description 7
- 230000003179 granulation Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 6
- 125000003710 aryl alkyl group Chemical group 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 5
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940050176 methyl chloride Drugs 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000008188 pellet Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 229910000091 aluminium hydride Inorganic materials 0.000 description 3
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 3
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical group O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 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 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000002075 main ingredient Substances 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229940095068 tetradecene Drugs 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 2
- 239000004914 cyclooctane Substances 0.000 description 2
- 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 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- PSOUOKYUENGTOA-UHFFFAOYSA-N ethene;dihydrochloride Chemical group Cl.Cl.C=C PSOUOKYUENGTOA-UHFFFAOYSA-N 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 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
- 230000004927 fusion Effects 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229940038384 octadecane Drugs 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UMGSEJIUITWVEP-UHFFFAOYSA-N 1-cyclopenta-2,4-dien-1-yl-2-phenylbenzene Chemical compound C1=CC(C=C1)c1ccccc1-c1ccccc1 UMGSEJIUITWVEP-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- IEJUDCCSASQBJM-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid;octadecane Chemical compound CCCCCCCCCCCCCCCCCC.CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O IEJUDCCSASQBJM-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MDBYTIXUOCNDNG-UHFFFAOYSA-N C1(C=CC2=CC=CC=C12)C1=C(C=CC=C1)C1=CC=CC=C1.C=C Chemical compound C1(C=CC2=CC=CC=C12)C1=C(C=CC=C1)C1=CC=CC=C1.C=C MDBYTIXUOCNDNG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920004449 Halon® Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- LOKPKYSOCCPWIZ-UHFFFAOYSA-N cacodyl oxide Chemical compound C[As](C)O[As](C)C LOKPKYSOCCPWIZ-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- CYKLGTUKGYURDP-UHFFFAOYSA-L copper;hydrogen sulfate;hydroxide Chemical compound O.[Cu+2].[O-]S([O-])(=O)=O CYKLGTUKGYURDP-UHFFFAOYSA-L 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- QPJORFLSOJAUNL-UHFFFAOYSA-N dibenzo[a,d][7]annulene Chemical compound C1=CC2=CC=CC=C2CC2=CC=CC=C21 QPJORFLSOJAUNL-UHFFFAOYSA-N 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- WRQYSUUIWDCBFZ-UHFFFAOYSA-N ethene;methanesulfonic acid Chemical group C=C.CS(O)(=O)=O WRQYSUUIWDCBFZ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000003325 follicular Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000005447 octyloxy 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])O* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012207 quantitative assay Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an ethylene copolymer composition (A') Comprising an ethylene/alpha-olefin copolymer (B) and an ethylene/alpha-olefin copolymer (C), said copolymers (B) and (C) having specific properties, said ethylene copolymer composition (A') having the following properties: the Melt Tension (MT) and the Melt Flow Rate (MFR) satisfy 9.0 XMFR-0.65＞MT＞2.2×MFR-0.84Activation energy of flow ((Ea). times.10)-4J/molK), the number of carbon atoms of 1-hexene (C) in the copolymers (B) and (C) and the total content of 1-hexene (x% by mole) in the copolymers (B) and (C) satisfy (0.039 Ln (C-2) +0.0096) x +2.87 < (Ea) x 10-4Not more than (0.039 Ln (C-2) + 0.1660). times.x +2.87, and the haze of a blown film made from the copolymer composition satisfies specific conditions. The ethylene copolymer composition is excellent in moldability, and a film excellent in transparency and mechanical strength can be obtained.
Description
The application is the dividing an application that be on December 25th, 1998, denomination of invention the applying date for the application for a patent for invention CN98126228.7 of " ethylene/alpha-olefin copolymer and preparation method thereof ".
Technical field
The present invention relates to a kind of ethylene/alpha-olefin copolymer, relate to the ethylene/alpha-olefin copolymer that a kind of formability is good, can make the good film of transparency and physical strength more specifically.The invention still further relates to a kind of ethylene copolymer composition, the content and the purposes of its content and purposes and ethylene/alpha-olefin copolymer are basic identical.
The invention still further relates to the composition that comprises ethylene/alpha-olefin copolymer or ethylene copolymer composition and another kind of ethylene copolymer.
The invention still further relates to the method for preparing ethylene/alpha-olefin copolymer.
Background technology
Ethylene copolymer can carry out moulding and be used for many fields with various forming methods.The required performance of ethylene copolymer has nothing in common with each other according to the purposes of forming method and multipolymer.For example, be equipped with the high-speed molding legal system in the process of blown film, must selecting its molecular weight to have the ethylene copolymer of high melt tension, stably carrying out high-speed molding and swing of film bubble or film follicular rupture do not take place.Need similar performance in blow moulding, to be used for preventing to hang from above or break, perhaps in the T shape die head method of forming, be used for making width to reduce and be reduced to minimum.
In open No.90810/1981 of Japanese Patent or No.106806/1985, reported by using Z-type catalyst (concrete is titanium catalyst) to improve polyvinyl melt tension or ratio of expansion (die swelling ratio), improved the processability of polymkeric substance.Yet the ethene polymers (specifically being low density ethylene copolymer) that uses titanium catalyst to obtain has wide composition usually and distributes, and contains the component that causes viscosity when polymkeric substance is used as moulding product (as film).Therefore, need to reduce the component that causes viscosity.
In the ethene polymers that makes with Z-type catalyst, those ethene polymerss that make with chrome catalysts have higher melt tension.But also need thermostability is further improved.
Melt tension height, the good heat stability of the many ethylene copolymers that obtain with olefin polymerization catalysis (comprising the transition metal metallocene compound) are the multipolymers that can satisfy above-mentioned requirements so estimate them.Yet in the ethylene copolymer that makes with metallocene catalyst, (melt tension's melt tension usually MT) is directly proportional with flow-activation energy (Ea).
As mentioned above, the polymkeric substance that melt tension is high shows good formability owing to bubble stability is good, but they have high flow-activation energy (Ea), this means that their condition of molding temperature influence is very big.Therefore, if can not be very strict and control condition of molding equably, the mold compound of gained can be inhomogeneous so.For example, the transparency of film is low.
When flow-activation energy (Ea) is low, can suppress the generation of ununiformity in the mold compound, but because melt tension is low, so can produce unsettled film bubble, thus processability descends.
Summary of the invention
The present invention makes in these cases, an object of the present invention is to provide a kind of ethylene/alpha-olefin copolymer, and it has good processability, can make the good film of transparency and physical strength.Another object of the present invention provides a kind of ethylene copolymer composition, and the content and the purposes of its content and purposes and ethylene/alpha-olefin copolymer are basic identical.
Ethylene/alpha-olefin copolymer of the present invention (A) is ethene and the multipolymer that contains the alpha-olefin of 6 to 8 carbon atoms, and it has following character:
(A-i) melt tension (MT) 190 ℃ time the and melt flow rate (MFR) (MFR) satisfy following relation:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84
(A-ii) flow-activation energy ((Ea) * 10 of determining by the synergetic shift factor of the time-temperature of flow curve
-4J/molK), relation below the content of alpha-olefin (x% mole) satisfies in carbonatoms of alpha-olefin (C) and the multipolymer in the multipolymer:
(0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1660) * x+2.87 and
(A-iii) mist degree (haze) of the film of 30 micron thickness that made with blow moulding by described multipolymer meets the following conditions:
Flow index (FI) (is defined as that shear-stress reaches 2.4 * 10 when at 190 ℃
6Dynes per centimeter
2(dyne/cm
2) time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI 〉=100 * MFR,
Be under 6 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
Be under 7 or 8 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.50/ (1-d) * log (3 * MT
1.4),
And
Flow index (FI) (is defined as in the time of 190 ℃ when shear-stress and reaches 2.4 * 10
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI＜100 * MFR,
Be under 6 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.25/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
Be under 7 or 8 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.50/ (1-d) * log (3 * MT
1.4),
Wherein, d represents density (gram per centimeter
3), MT represents melt tension (gram).
Ethylene/alpha-olefin copolymer of the present invention (A) can obtain by in the presence of olefin polymerization catalysis ethene being carried out copolymerization with the alpha-olefin that contains 6 to 8 carbon atoms, and described catalyzer comprises:
(a) Organoaluminoxy compound
(b-I) at least a transistion metal compound that is selected from by the transistion metal compound of following formula (I) expression:
ML
1 x (I)
Wherein, M is the transition metal atoms that is selected from periodictable the 4th family; L
1Be and transition metal atoms M coordinate ligand, at least two ligand L
1Respectively do for oneself and contain the cyclopentadienyl of the replacement that is selected from 3 to 10 at least one groups in the carbon atom alkyl, the ligand L except that the cyclopentadienyl that replaces
1Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom; X is the valency of transition metal atoms M;
And
(b-II) at least a transistion metal compound that is selected from by the transistion metal compound of following formula (II) expression:
ML
2 x (II)
Wherein, M is the transition metal atoms that is selected from periodictable the 4th family; L
2Be and transition metal atoms M coordinate ligand, at least two ligand L
2Respectively do for oneself methyl cyclopentadienyl or ethyl cyclopentadienyl, the ligand L except that methyl cyclopentadienyl or ethyl cyclopentadienyl
2Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom; X is the valency of transition metal atoms M.
Olefin polymerization catalysis also comprises the carrier (c) of load Organoaluminoxy compound (a), transistion metal compound (b-I) and transistion metal compound (b-II) preferably.
The processability of ethylene/alpha-olefin copolymer (A) is good, can make the good film of transparency and physical strength.
Ethylene copolymer composition of the present invention (A ') has and essentially identical content of ethylene/alpha-olefin copolymer and purposes, and described composition comprises:
(B) ethylene/alpha-olefin copolymer and
(C) ethylene/alpha-olefin copolymer,
Described ethylene/alpha-olefin copolymer (B) is ethene and the multipolymer that contains the alpha-olefin of 6 to 8 carbon atoms, has following character:
(B-i) density is at the 0.880-0.970 gram per centimeter
3Scope in,
(B-ii) in the melt flow rate (MFR) (MFR) under 190 ℃, 2.16 kilograms the load in/10 minutes scope of 0.02-200 gram,
(B-iii) component mark (W) and the density (d) that is dissolved in decane under the room temperature satisfies following relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.26* exp (100 (d-0.88))+0.1
(B-iv) temperature (Tm) of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and density (d) satisfy following relation:
Tm＜400×d-248，
(B-v) melt tension (MT) 190 ℃ time the and melt flow rate (MFR) (MFR) satisfy following relation:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
(B-vi) flow-activation energy ((Ea) * 10 of determining by the synergetic shift factor of the time-temperature of flow curve
-4J/molK), relation below the content of alpha-olefin (x% mole) satisfies in carbonatoms of alpha-olefin (C) and the multipolymer in the multipolymer: (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1660) * x+2.87
And
(B-vii) weight-average molecular weight (M that records by GPC
w) and number-average molecular weight (M
n) ratio (M
w/ M
n) satisfy
Following condition:
2.2＜M
w/M
n＜3.5；
Described ethylene/alpha-olefin copolymer (C) is ethene and the multipolymer that contains the alpha-olefin of 6 to 8 carbon atoms, has following character:
(C-i) density is at the 0.880-0.970 gram per centimeter
3Scope in,
(C-ii) in the melt flow rate (MFR) (MFR) under 190 ℃, 2.16 kilograms the load in/10 minutes scope of 0.02-200 gram,
(C-iii) component mark (W) and the density (d) that is dissolved in decane under the room temperature satisfies following relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.26* exp (100 (d-0.88))+0.1
(C-iv) temperature (Tm) of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and density (d) satisfy following relation:
Tm＜400×d-248，
And
(C-v) melt tension (MT) 190 ℃ time the and melt flow rate (MFR) (MFR) satisfy following relation:
MT≤2.2×MFR
-0.84；
Wherein, the melt flow rate (MFR) of multipolymer (C) (MFR (C)) meets the following conditions with the ratio of the melt flow rate (MFR) (MFR (B)) of multipolymer (B):
1＜(MFR(C))/(MFR(B))≤20。
Be preferably the ethylene/alpha-olefin copolymer (B) in the ethylene copolymer composition (A ') and (C) all be ethene/1-hexene copolymer, in this case, ethylene copolymer composition (A ') has following character:
(A '-i) melt tension (MT) and the melt flow rate (MFR) (MFR) 190 ℃ the time meets the following conditions:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
(A '-ii) by definite flow-activation energy ((Ea) * 10 of the synergetic shift factor of the time-temperature of flow curve
-4J/molK), multipolymer (B) and (C) in the carbonatoms (C) of 1-hexene and multipolymer (B) and (C) in the total content (x% mole) of 1-hexene concern below satisfying:
(0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1660) * x+2.87 and
(A '-mist degree of the film of 30 micron thickness that iii) made with blow moulding by described copolymer compositions meets the following conditions:
Flow index (FI) (is defined as that shear-stress reaches 2.4 * 10 when at 190 ℃
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI 〉=100 * MFR,
Mist degree＜0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
And
Flow index (FI) (is defined as in the time of 190 ℃ when shear-stress and reaches 2.4 * 10
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI＜100 * MFR,
Mist degree＜0.25/ (1-d) * log (3 * MT
14) * (C-3)
0.1
Wherein, d represents density (gram per centimeter
3), MT represents melt tension (gram), C represents the carbonatoms of 1-hexene, and promptly 6.
Ethylene copolymer composition (A ') except character (A '-i) to (A '-iii), also have following character preferably:
(A '-weight-average molecular weight (M that iv) records by GPC
w) and number-average molecular weight (M
n) ratio (M
w/ M
n) meet the following conditions:
2.0≤M
w/M
n≤2.5。
Ethylene/alpha-olefin copolymer of the present invention (A) or ethylene copolymer composition of the present invention (A ') can with following material blend:
(D) ethylene/alpha-olefin copolymer that in the presence of olefin polymerization catalysis, obtains by ethene and the alpha-olefin copolymer that contains 3 to 20 carbon atoms, described catalyzer comprises (a) Organoaluminoxy compound and (b-III) contains the transistion metal compound of periodictable the 4th group 4 transition metal of the ligand with cyclopentadienyi skeleton, and described ethylene/alpha-olefin copolymer has following character:
(D-i) density is at the 0.850-0.980 gram per centimeter
3Scope in and
(D-ii) limiting viscosity (η) that records in naphthane 135 ℃ the time is in the scope of 0.4-8dl/g;
Condition is that ethylene/alpha-olefin copolymer (A) is different from ethylene/alpha-olefin copolymer (D), ethylene/alpha-olefin copolymer (B) and (C) all be different from ethylene/alpha-olefin copolymer (D).
The preparation method of ethylene/alpha-olefin copolymer of the present invention comprises: make ethene and the alpha-olefin that contains 6 to 8 carbon atoms carry out copolymerization in the presence of above-mentioned olefin polymerization catalysis, described catalyzer comprises (a) Organoaluminoxy compound, (b-I) transistion metal compound and (b-II) transistion metal compound.
Description of drawings
Fig. 1 is the figure of the preparation process of the used olefin polymerization catalysis of explanation the present invention.
Embodiment
Below describe ethylene/alpha-olefin copolymer of the present invention (A) and preparation method thereof in detail, and ethylene copolymer composition (A ').
Term used herein " polymerization " is not limited to " homopolymerization ", also can be regarded as " copolymerization ".Similarly, term " polymer " used herein " be not limited to " homopolymer ", also can be regarded as " multipolymer ".
Ethylene/alpha-olefin copolymer (A)
Ethylene/alpha-olefin copolymer of the present invention (A) is ethene and the random copolymers that contains the alpha-olefin of 6 to 8 carbon atoms.The example that is used for carrying out the alpha-olefin that contains 6 to 8 carbon atoms of copolymerization with ethene is preferably and comprises unbranched linear alpha-olefin, as 1-hexene, 1-heptene and 1-octene.Wherein preferably use the 1-hexene.
Ethylene/alpha-olefin copolymer of the present invention (A) has following character (A-i) to (A-iii):
(A-i) melt tension (MT (gram)) and melt flow rate (MFR) (MFR (restraining/10 minutes)) satisfy following relation:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
Be preferably 9.0 * MFR
-0.65＞MT＞2.3 * MFR
-0.84,
Be more preferably 8.5 * MFR
-0.65＞MT＞2.5 * MFR
-0.84
Has good processability so have the melt tension height of the ethylene/alpha-olefin copolymer of above character.
MFR is to be that 2.16 kilograms, temperature are to record under 190 ℃ the condition according to ASTMD1238-65T at load.
Melt tension (MT) is that the stress that records by with constant rate of speed stretching molten polymer the time is determined.That is to say, the polymer powder that makes with ordinary method fusion and granulation, is obtained testing sample.Then the MT measuring engine made from ToyoSeiki Seisakusho K.K., be that 190 ℃, extruding rate be that 15 mm/min, rate of withdraw (take-up rate) they are 10 to 20 meters/minute, to annotate outspoken footpath be 2.09mm , annotate mouth length are the melt tension of 8 millimeters conditioned measurement sample at resin temperature.Before granulation, with ethylene/alpha-olefin copolymer and 0.05% (weight) tricresyl phosphate (2, the 4-di-tert-butyl-phenyl) ester (as auxiliary antioxidant), 0.1% (weight) 3-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid Octadecane base ester (as thermo-stabilizer) and 0.05% (weight) calcium stearate (as hydrochloric acid absorbent) blend.
(A-ii) flow-activation energy ((Ea) * 10 of determining by the synergetic shift factor of the time-temperature of flow curve
-4J/molK), relation below the content of alpha-olefin (x% mole) satisfies in carbonatoms of alpha-olefin (C) and the multipolymer in the multipolymer: (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1660) * x+2.87
Be preferably (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1500) * x+2.87
Be more preferably (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1300) * x+2.87
In order to improve the film forming performance of moulding, need to improve melt tension, be the effective ways of known raising melt tension and introduce the long-chain side chain.The Ea of the ethylene/alpha-olefin copolymer of no long-chain side chain represents with following formula: Ea * 10
-4=(0.039 Ln (C-2)+0.0096) * x+2.87. is when existing the long-chain side chain, and the Ea value increases, so if Ea * 10
-4＞(0.039 Ln (C-2)+0.0096) * x+2.87 then just thinks to have the long-chain side chain, is molded into film properties and transparency all is improved.In Ea * 10
-4Under the situation of＞(0.039 Ln (C-2)+0.1660) * x+2.87, although processability is good, film toughness and film transparency have all reduced, so this situation is unfavorable.
The measurement of flow-activation energy (Ea) for example is described in " polymkeric substance experimental science; the 9th volume; thermodynamic property I " (Polymer Experimental Science, Vol.9, Thermodynamic Properties I), polymkeric substance experimental science editorial board by polymkeric substance association edits, Kyoritsu Publishing K.K., 25-28 page or leaf.The flow curve that the relation of measurement visco-elasticity and frequency obtains is determined flow-activation energy (Ea) by the synergetic shift factor of the time-temperature of flow curve.Record the figure that expression energy storage Young's modulus (ordinate zou) and circular frequency (X-coordinate) concern fixedly the time at some basal temperature.Then, the data that will record when different measurement temperature move along the direction parallel with X-coordinate, as a result on their overlapping data that obtain when being basal temperature (simplification of thermorheology).The displacement Log (aT) that the data that obtain under the measurement temperature are overlapped onto on the data that obtain under the basal temperature maps to the 1/T reciprocal that measures temperature (absolute temperature), obtains straight slope.This straight slope be multiply by 2.303R (R is a gas law constant), obtain temperature independent activation energy constant thus.
Particularly, the following measurement of Ea.
Energy storage visco-elasticity during measured angular speed (ω (rad/sec)) (G ' (dynes per centimeter
2)) distribution.The parallel plate that is 25mm with a diameter is used as sample holder.Sample thickness is about 2 millimeters.Measuring temperature is 130,170,200 and 230 ℃, under each temperature, measure G ' in the scope of 0.04≤ω≤400.For example, when 130 ℃ measurement, sample is heated to 150 ℃ with complete fusion crystal, is cooled to 130 ℃ then.Suitably select strain in the scope of 2-25%, so that torque is can be detected in useful range, and it is very big can not become.After the measurement, 130 ℃ stacked as basal temperature, the flow curve that will under four kinds of temperature condition, obtain, from the Arrhenius type curve of shift factor, calculate the Ea value.Calculate with the RHIOS analysis software that is connected on the RDS-II.
(A-iii) mist degree of the film of 30 micron thickness that made with blow moulding by described multipolymer meets the following conditions:
Flow index (FI) (is defined as in the time of 190 ℃ when shear-stress and reaches 2.4 * 10
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI 〉=100 * MFR,
Be under 6 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
Be under 7 or 8 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.50/ (1-d) * log (3 * MT
1.4),
And
Flow index (FI) (is defined as in the time of 190 ℃ when shear-stress and reaches 2.4 * 10
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI＜100 * MFR,
Be under 6 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.25/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
Be under 7 or 8 the situation at the carbonatoms (C) of alpha-olefin,
Mist degree＜0.50/ (1-d) * log (3 * MT
1.4),
Wherein, d represents density (gram per centimeter
3), MT represents melt tension (gram).
The ethylene/alpha-olefin copolymer that satisfies above condition has good processability, can make the good film of transparency.
Condition lower edge kapillary extrusion resin changing shearing rate finds the shearing rate corresponding with specifying stress, so determines flow index.That is to say, use the sample identical, be that 190 ℃, shear-stress are about 5 * 10 at resin temperature with the MT measurement
4To 3 * 10
6Dynes per centimeter
2Condition under, measure flow index with Capillary Flow property test machine (making) by Toyo Selki Seisakusho K.K..
In this was measured, the diameter of mouth was annotated in following variation according to the MFR (restraining/10 minutes) of resin to be measured:
MFR＞20:0.5 millimeter
20 〉=MFR＞3:1.0 millimeter
3 〉=MFR＞0.8:2.0 millimeter
0.8 〉=MFR:3.0 millimeter
Measuring density (d) as follows.To under 190 ℃, 2.16 kilogram load, measure the line material (strands) that obtains in melt flow rate (MFR) (MFR) process in 120 ℃ of heating 1 hour, be cooled to room temperature lentamente through 1 hour then, with the density of density gradient tube measuring line material.
Ethylene/alpha-olefin copolymer of the present invention (A) is preferably, except above-mentioned character also comprises following character.
In ethylene/alpha-olefin copolymer of the present invention (A), requirement is 50-100% (weight), is preferably 55-99% (weight) by the unitary amount of component that ethene obtains, be more preferably 65-98% (weight), best is 70-96% (weight), the unitary amount of component that is obtained by the alpha-olefin that contains 6 to 8 carbon atoms is 0-50% (weight), be preferably 1-45% (weight), be more preferably 2-35% (weight), good especially is 4-30% (weight).
The composition of ethylene/alpha-olefin copolymer is measured usually with the following methods.At diameter is in the test tube of 10mm about 200 milligrams of multipolymers to be solved homogeneously in 1 milliliter of hexachlorobutadiene with the preparation sample, measuring temperature is that 120 ℃, survey frequency are that 25.05Mhz, spectrum width are 1,500Hz, pulse repetition time are 4.2 seconds, and pulse width is a measure sample under the measuring condition of 6 microseconds
13The C-NMR spectrum.
The density (d) of ethylene/alpha-olefin copolymer (A) is preferably the 0.880-0.970 gram per centimeter
3, be preferably the 0.880-0.960 gram per centimeter
3, be more preferably the 0.890-0.935 gram per centimeter
3, best is the 0.905-0.930 gram per centimeter
3
The melt flow rate (MFR) (MFR) of ethylene/alpha-olefin copolymer (A) is preferably 0.02-200 gram/10 minutes, is preferably 0.05-50 gram/10 minutes, is more preferably 0.1-10 gram/10 minutes.
The component mark (W) and the density (d) that are dissolved in n-decane in the ethylene/alpha-olefin copolymer in the time of 23 ℃ (A) are preferably satisfied following relation:
Under MFR≤situation of/10 minutes of 10 grams,
W＜80×exp(-100(d-0.88))+0.1，
Be preferably W＜60 * exp (100 (d-0.88))+0.1,
Be more preferably W＜40 * exp (100 (d-0.88))+0.1,
Under MFR＞situation of/10 minutes of 10 grams,
W＜80×(MFR-9)
0.26×exp(-100(d-0.88))+0.1
Be dissolved in the following measurement of component mark (W) of n-decane in the ethylene/alpha-olefin copolymer: 3 gram multipolymers are added in 450 milliliters of n-decanes of people, be dissolved in wherein in 145 ℃, be cooled to 23 ℃ again.Then, remove by filter the part that is insoluble to n-decane, from filtrate, reclaim the part that is dissolved in n-decane.
The little multipolymer of component mark that is dissolved in n-decane has narrow component and distributes.
The temperature of the ethylene/alpha-olefin copolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) (Tm, (℃)) and density (d, (gram per centimeter
3)) need to satisfy following the relation:
Tm＜400×d-248，
Be preferably Tm＜450 * d-296,
Be more preferably Tm＜500 * d-343,
That good especially is Tm＜550 * d-392.
The temperature (Tm) of the ethylene/alpha-olefin copolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) obtains from endothermic curve.The following acquisition of this endothermic curve: in the aluminium dish with about 5 milligrams of samples with the heating of 10 ℃/minute speed until 200 ℃, sample remain in 200 ℃ about 5 minutes, its speed with 20 ℃/minute is cooled to room temperature, again with 10 ℃/minute speed heating.The DSC-7 type instrument that in measurement, uses perkin-ElmerCo. to make.
The ethylene/alpha-olefin copolymer that has the relation that is defined as above between component mark (W) that has the relation that is defined as above and be dissolved in n-decane between the temperature of the endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and the density (d) and density (d) has narrow component and distributes.
Above-mentioned ethylene/alpha-olefin copolymer (A) can two or more be used in combination.
Ethylene/alpha-olefin copolymer of the present invention (A) can carry out copolymerization to ethene with the alpha-olefin that contains 6 to 8 carbon atoms and obtain in the presence of olefin polymerization catalysis (Cat-1), described catalyzer (Cat-1) is formed by following material:
(a) Organoaluminoxy compound,
(b-I) at least a transistion metal compound that is selected from the transistion metal compound shown in the chemical formula (I),
(b-II) at least a transistion metal compound that is selected from the transistion metal compound shown in the chemical formula (II).
Olefin polymerization catalysis also comprises load (a) Organoaluminoxy compound, (b-I) at least a transistion metal compound of the transistion metal compound shown in the chemical formula (I) and (b-II) at least a carrier (c) that is selected from the transistion metal compound of the transistion metal compound shown in the chemical formula (II) of being selected from.Hereinafter sometimes this carried catalyst is called " Cat-2 ".
It is as follows to be used to form olefin polymerization catalysis (Cat-1) and component (Cat-2).
(a) Organoaluminoxy compound
Being used for Organoaluminoxy compound of the present invention (a) (hereinafter being called " component (a) " sometimes) can be the hitherto known aikyiaiurnirsoxan beta (aluminoxane) of benzene or the benzene-insoluble Organoaluminoxy compound that discloses as the open No.276807/1990 of Japanese Patent of being dissolved in.
Aikyiaiurnirsoxan beta can prepare with the following method, and the form with its hydrocarbon solution obtains usually.
(1) organo-aluminium compound (as trialkylaluminium) is added contains the compound of planar water or contain in the hydrocarbon medium suspension of salt (as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, single nickel salt hydrate or Cerium II Chloride hydrate) of crystal water, so that described organo-aluminium compound and planar water or crystal water react.
(2) in medium (as benzene, toluene, ether or tetrahydrofuran (THF)), water, ice or water vapour are acted directly on the organo-aluminium compound (as trialkylaluminium).
(3) organotin oxides (as cacodyl oxide base tin or dibutyltin oxide) and organo-aluminium compound (as trialkylaluminium) are reacted.
Aikyiaiurnirsoxan beta can contain a spot of organo-metallic component.Can from the aluminoxanes solution that reclaims, distillation residuum be dissolved in the solvent again except that desolvating or unreacted organo-aluminium compound.
The example that is used to prepare the organo-aluminium compound of aikyiaiurnirsoxan beta comprises, trialkylaluminium is as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three amyl group aluminium, three hexyl aluminium, trioctylaluminum and three decyl aluminium; Tricyclic alkyl aluminium is as thricyclohexyl aluminium and three ring octyl group aluminium; Aluminum dialkyl monohalide is as a Chlorodimethyl aluminium, aluminium diethyl monochloride, monobromo diethyl aluminum and a chloro-di-isobutyl aluminum; The hydrogenation aluminum dialkyl is as diethyl aluminium hydride and diisobutylaluminium hydride; The alkoxyl group aluminum dialkyl is as methoxyl group dimethyl aluminium and oxyethyl group diethyl aluminum; The aryloxy aluminum dialkyl is as the phenoxy group diethyl aluminum.
Wherein, good especially is trialkylaluminium and tricyclic alkyl aluminium.
What can also be used as organo-aluminium compound is the prenyl aluminium (isoprenylaluminum) shown in the following formula:
(i-C
4H
9)
xAl
y(C
5H
10)
z
Wherein, x, y, z are positive numbers, and z 〉=2x.
Above-mentioned organo-aluminium compound can use separately or be used in combination.
The example that is used to prepare the solvent of aikyiaiurnirsoxan beta comprises aromatic hydrocarbons, as benzene,toluene,xylene, isopropyl benzene and cymene; Aliphatic hydrocrbon is as pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane and octadecane; Alicyclic hydrocarbon is as pentamethylene, hexanaphthene, cyclooctane and methylcyclopentane; Petroleum fractions is as gasoline, kerosene and gas oil; These aromatic hydrocarbons, aliphatic hydrocrbon and alicyclic halogenated products are as their chlorination or brominated product. and what can also use is ethers, as ether and tetrahydrofuran (THF).In these solvents, good especially is aromatic hydrocarbons.
Be dissolved in the Al component of benzene when can be used for contained 60 ℃ of benzene-insoluble Organoaluminoxy compound of the present invention, in the Al atom, its content is no more than 10%, is preferably and is no more than 5%, good especially is to be no more than 2%, and this Organoaluminoxy compound is insoluble to or is dissolved in the benzene on a small quantity.
The solubleness of Organoaluminoxy compound in benzene can be measured with following method.The Organoaluminoxy compound that will be equivalent to 100 milligram-atom Al is suspended in 100 milliliters of benzene, mixes 6 hours in 60 ℃.With the G-5 glass filter that chuck is arranged mixture is carried out heat filtering in 60 ℃ then, in the 60 ℃ of solids wash that will on strainer, separate to obtain 4 times, obtain filtrate with 50 milliliters of benzene.Measure the amount (x mmole) of existing Al atom in whole filtrates, obtain solubleness (x%).
(b-I) transistion metal compound and (b-II) transistion metal compound
Being used for transistion metal compound of the present invention (b-I) is the transistion metal compound shown in the following formula (I), and being used for transistion metal compound of the present invention (b-II) is the transistion metal compound shown in the following formula (II).
ML
1 x(I) wherein, M is the transition metal atoms that is selected from periodictable the 4th family; L
1Be and transition metal atoms M coordinate ligand, at least two ligand L
1Respectively do for oneself and contain the cyclopentadienyl of the replacement that is selected from 3 to 10 at least one groups in the carbon atom alkyl, the ligand L except that the cyclopentadienyl that replaces
1Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom; X is the valency of transition metal atoms M.
ML
2 x (II)
Wherein, M is the transition metal atoms that is selected from periodictable the 4th family; L
2Be and transition metal atoms M coordinate ligand, at least two ligand L
2Respectively do for oneself methyl cyclopentadienyl or ethyl cyclopentadienyl, the ligand L except that methyl cyclopentadienyl or ethyl cyclopentadienyl
2Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom; X is the valency of transition metal atoms M.
Below describe in detail by chemical formula (I) and the transistion metal compound (II) represented.
In chemical formula (I), M is the transition metal atoms that is selected from periodictable the 4th family, specifically is zirconium, titanium or hafnium, is preferably zirconium.
L
1Be and transition metal atoms M coordinate ligand, at least two ligand L
1Respectively do for oneself and contain the cyclopentadienyl of the replacement that is selected from 3 to 10 at least one groups in the carbon atom alkyl.These ligands L
1Can be identical or different.
The cyclopentadienyl that replaces can have two or more substituting groups, and these two or multiple substituting group can be identical or different.When the cyclopentadienyl that replaces had two or more substituting group, at least one substituting group was the alkyl that contains 3 to 10 carbon atoms, and remaining substituting group is methyl, ethyl or the alkyl that contains 3 to 10 carbon atoms.
The example that contains the alkyl of 3 to 10 carbon atoms comprises, alkyl, cycloalkyl, aryl and aralkyl.Specifically, alkyl can be arranged, as n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, 2-ethylhexyl and decyl; Cycloalkyl is as cyclopentyl and cyclohexyl; Aryl is as phenyl and tolyl; Aralkyl is as benzyl and neophyl (neophyl).
Wherein, be preferably alkyl, good especially is n-propyl and normal-butyl.Be preferably dibasic cyclopentadienyl with the cyclopentadienyl of the replacement of transition-metal coordination, good especially is 1, the cyclopentadienyl that 3-replaces.
In chemical formula (I), the ligand L except that the cyclopentadienyl that replaces with transition metal atoms M coordinate
1Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom.
The example that contains the alkyl of 1 to 12 carbon atom comprises, alkyl, cycloalkyl, aryl and aralkyl.Specifically, alkyl can be arranged, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl, octyl group, 2-ethylhexyl and decyl; Cycloalkyl is as cyclopentyl and cyclohexyl; Aryl is as phenyl and tolyl; Aralkyl is as benzyl and neophyl.
The example of alkoxyl group comprises, methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, pentyloxy, hexyloxy and octyloxy.
Examples of aryloxy comprises phenoxy group.
The example of trialkylsilkl comprises, trimethyl silyl, triethylsilyl and triphenyl silyl.
Halogen atom is fluorine, chlorine, bromine or iodine.
Example by the transistion metal compound of chemical formula (I) expression comprises,
Dichloride two (n-propyl cyclopentadienyl) close zirconium,
Dichloride two (n-butyl cyclopentadienyl) close zirconium,
Dichloride two (n-hexyl cyclopentadienyl) close zirconium,
Dichloride two (methyl n-propyl cyclopentadienyl) close zirconium,
Dichloride two (methyl n-butyl cyclopentadienyl) close zirconium,
Dichloride two (dimethyl n-butyl cyclopentadienyl) close zirconium,
Dibrominated two (n-butyl cyclopentadienyl) close zirconium,
Chlorination methoxyl group two (n-butyl cyclopentadienyl) close zirconium,
Chlorination oxyethyl group two (n-butyl cyclopentadienyl) close zirconium,
Chlorination butoxy two (n-butyl cyclopentadienyl) close zirconium,
Diethoxy two (n-butyl cyclopentadienyl) close zirconium,
Methyl chloride two (n-butyl cyclopentadienyl) close zirconium,
Dimethyl two (n-butyl cyclopentadienyl) close zirconium,
Zephiran chloride two (n-butyl cyclopentadienyl) close zirconium,
Dibenzyl two (n-butyl cyclopentadienyl) close zirconium,
Chlorination phenyl two (n-butyl cyclopentadienyl) close zirconium and
Zirconium is closed in hydrogenation chlorination two (n-butyl cyclopentadienyl).
In above these examples, dibasic cyclopentadienyl rings comprises 1,2-and 1, and the cyclopentadienyl rings that 3-replaces, trisubstituted cyclopentadienyl rings comprises 1,2,3-and 1,2, the cyclopentadienyl rings that 4-replaces.
Can also be used for transistion metal compound of the present invention is the transistion metal compound that the zirconium metal of above-mentioned zirconium compounds is replaced with titanium metal or hafnium metal.
In the transistion metal compound of chemical formula (I) expression, dichloride two (n-propyl cyclopentadienyl) that good especially is closes that zirconium, dichloride two (n-butyl cyclopentadienyl) close zirconium, dichloride two (1-methyl-3-n-propyl cyclopentadienyl) closes zirconium and dichloride two (1-methyl-3-n-butyl cyclopentadienyl) is closed zirconium.
In chemical formula (II), M is the transition metal atoms that is selected from periodictable the 4th family, and concrete is zirconium, titanium or hafnium, is preferably zirconium.
L
2Be and transition metal atoms M coordinate ligand, at least two ligand L
2Respectively do for oneself methyl cyclopentadienyl or ethyl cyclopentadienyl.These ligands L
2Can be identical or different.
In chemical formula (II), the ligand L except that methyl cyclopentadienyl and ethyl cyclopentadienyl
2Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom, each in them all with chemical formula (I) in L
1Pointed group or atom are identical.
Example by the transistion metal compound of chemical formula (II) expression comprises,
Dichloride two (methyl cyclopentadienyl) close zirconium,
Dichloride two (ethyl cyclopentadienyl) close zirconium,
Dibrominated two (methyl cyclopentadienyl) close zirconium,
Dibrominated two (ethyl cyclopentadienyl) close zirconium,
Chlorination methoxyl group two (methyl cyclopentadienyl) close zirconium,
Chlorination methoxyl group two (ethyl cyclopentadienyl) close zirconium,
Chlorination oxyethyl group two (methyl cyclopentadienyl) close zirconium,
Chlorination oxyethyl group two (ethyl cyclopentadienyl) close zirconium,
Diethoxy two (methyl cyclopentadienyl) close zirconium,
Diethoxy two (ethyl cyclopentadienyl) close zirconium,
Methyl chloride two (methyl cyclopentadienyl) close zirconium,
Methyl chloride two (ethyl cyclopentadienyl) close zirconium,
Dimethyl two (methyl cyclopentadienyl) close zirconium,
Dimethyl two (ethyl cyclopentadienyl) close zirconium,
Zephiran chloride two (methyl cyclopentadienyl) close zirconium,
Zephiran chloride two (ethyl cyclopentadienyl) close zirconium,
Dibenzyl two (methyl cyclopentadienyl) close zirconium,
Dibenzyl two (ethyl cyclopentadienyl) close zirconium,
Chlorination phenyl two (methyl cyclopentadienyl) close zirconium,
Chlorination phenyl two (ethyl cyclopentadienyl) close zirconium,
Hydrogenation chlorination two (methyl cyclopentadienyl) close zirconium and
Zirconium is closed in hydrogenation chlorination two (ethyl cyclopentadienyl).
Can also be used for transistion metal compound of the present invention is the transistion metal compound that the zirconium metal of above-mentioned zirconium compounds is replaced with titanium metal or hafnium metal.
In the transistion metal compound of chemical formula (II) expression, good especially is that dichloride two (methyl cyclopentadienyl) is closed zirconium and dichloride two (ethyl cyclopentadienyl) is closed zirconium.
In the present invention; at least a transistion metal compound and at least a transistion metal compound that is selected from the transistion metal compound of chemical formula ( II ) expression that is selected from the transistion metal compound of chemical formula ( I ) expression is used in combination as the transistion metal compound component.MFR ( I ) /MFR ( II ) MFR ( I ) /MFR ( II ) ≤20,MFR ( I ) /MFR ( II ) ( I ) MFR ( MFR ( I ) ) ( II ) MFR ( MFR ( II ) ) 。
The example of these combinations comprises dichloride two (1,3-normal-butyl methyl cyclopentadienyl) closes zirconium and dichloride two (methyl cyclopentadienyl) and close the zirconium combination, dichloride two (1,3-n-propyl methyl cyclopentadienyl) close zirconium and dichloride two (methyl cyclopentadienyl) and close the zirconium combination, and dichloride two (n-butyl cyclopentadienyl) is closed zirconium and dichloride two (methyl cyclopentadienyl) is closed the zirconium combination.
It is at least a that to be selected from by the transistion metal compound (b-I) in the transistion metal compound of chemical formula (I) expression be that the mol ratio of (b-I)/(b-II) is 99/1 to 40/60 with at least a being selected from by the suitable consumption of the transistion metal compound (b-II) in the transistion metal compound of chemical formula (II) expression, be preferably 95/5 to 45/55, be more preferably 90/10 to 50/50, best is 85/15 to 55/45.
Comprise at least a being selected from and hereinafter be sometimes referred to as " component (b) " by transistion metal compound (b-I) in the transistion metal compound of chemical formula (I) expression and at least a transition metal compound catalyst component that is selected from by the transistion metal compound (b-II) in the transistion metal compound of chemical formula (II) expression.
Though what use in the present invention is the olefin polymerization catalysis (Cat-1) that is formed by Organoaluminoxy compound (a), transistion metal compound (b-I) and transistion metal compound (b-II), yet the catalyzer (Cat-2) that also available Organoaluminoxy compound (a), transistion metal compound (b-1) and transistion metal compound (b-II) load on the following carrier (c) replaces.
(c) carrier
Can randomly be used for carrier of the present invention is inorganic or the granular solids of organic compound, and particle diameter is the 10-300 micron, is preferably the 20-200 micron.Inorganic carrier is preferably porous oxide, and its example comprises SiO
2, Al
2O
3, MgO, ZrO
2, TiOZ
2, B
2O
3, CaO, ZnO, BaO, ThO
2, and their mixture, as SiO
2-MgO, SiO
2-Al
2O
3, SiO
2-TiO
2, SiO
2-V
2O
5, SiO
2-Cr
2O
3And SiO
2-TiO
2-MgO.Wherein, be preferably those and contain SiO
2And/or Al
2O
3Carrier as main ingredient.
Above-mentioned inorganic oxide can contain a spot of carbonate, vitriol, nitrate and oxide component, as Na
2CO
3, K
2CO
3, CaCO
3, MgCO
3, Na
2SO
4, Al
2(SO
4)
3, BaSO
4, KNO
3, Mg (NO
3)
2, Al (NO
3)
3, Na
2O, K
2O and Li
2O.
Though the character of carrier (c) changes with type and preparation method, be used for preferable carrier of the present invention and need have 50-1,000 meter
2/ gram (is preferably 100-700 rice
2/ gram) specific surface area, 0.3-2.5 centimetre
3The pore volume of/gram.If desired, carrier in 100 to 1,000 ℃ (being preferably 150 to 700 ℃) uses after the roasting down.
The amount of planar water is preferably less than 0.5% (weight) to be advisable less than 1.0% (weight) in the carrier (c).The amount of surface hydroxyl is advisable to be not less than 1.0% (weight) in the carrier (c), is preferably 1.5-4.0% (weight), and good especially is 2.0-3.5% (weight).
The following measurement of amount (% weight) of amount of planar water (% weight) and surface hydroxyl:
The amount of planar water
With carrier under atmospheric pressure, in stream of nitrogen gas, in 200 ℃ of dryings 4 hours.The weight that carrier is lost after drying is to the percentage ratio of weight before dry amount as planar water.
The amount of surface hydroxyl
Under atmospheric pressure, in stream of nitrogen gas, in the weight of 200 ℃ of dryings gained carrier after 4 hours as X (gram).With carrier in 1,000 ℃ of roasting 20 hours removing surface hydroxyl, gained through the weight of roasting carrier as Y (gram), the amount of surface hydroxyl is calculated with following formula:
The amount of surface hydroxyl (% weight)=(X-Y)/X} * 100
Can also as carrier (c) among the present invention be the granular solids of organic compound, particle diameter is the 10-300 micron.The example of these organic compound comprises the polymkeric substance (multipolymer) that makes as main ingredient with the alpha-olefin (as ethene, propylene, 1-butylene or 4-methyl-1-pentene) that contains 2 to 14 carbon atoms, and the polymkeric substance (multipolymer) that makes as main ingredient with vinyl cyclohexane or vinylbenzene.
Following organo-aluminium compound (d) can be randomly as forming used olefin polymerization catalysis (Cat-1) and component (Cat-2) among the present invention.
(d) organo-aluminium compound
The organo-aluminium compound that can randomly be used for the expression of organo-aluminium compound of the present invention (d) (hereinafter being sometimes referred to as " component (d) ") for example following chemical formula (i):
R
1 nAlX
3-n (i)
Wherein, R
1Be the alkyl that contains 1 to 12 carbon atom, X is halogen atom or hydrogen atom, and n is 1 to 3.
In chemical formula (i), R
1Be the alkyl that contains 1 to 12 carbon atom, as alkyl, cycloalkyl or aryl.The example of these groups comprises methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, amyl group, hexyl, octyl group, cyclopentyl, cyclohexyl, phenyl and tolyl.
The example of organo-aluminium compound (d) comprises trialkylaluminium, as trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, trioctylaluminum and three-2-ethylhexyl aluminium; Alkenyl aluminium is as prenyl aluminium; Aluminum dialkyl monohalide is as a Chlorodimethyl aluminium, aluminium diethyl monochloride, a chlorine di-isopropyl aluminium, a chloro-di-isobutyl aluminum and monobromo dimethyl aluminium; Sesquialkyl aluminium halogenide is as sesquialter methyl chloride aluminium, sesquialter ethylaluminium chloride, sesquialter chlorination sec.-propyl aluminium, sesquialter chlorinated butyl aluminium and sesquialter bromination aluminium triethyl; The dihalide aluminum alkyls is as dichloromethyl aluminium, ethyl aluminum dichloride, two chloro isopropyl aluminium and dibromo aluminium triethyl; Alkyl aluminium hydride is as diethyl aluminium hydride and diisobutylaluminium hydride.
What also can be used as organo-aluminium compound (d) is the compound that following chemical formula is (ii) represented:
R
1 nAlY
3-n (ii)
Wherein, R
1As mentioned above, Y is-OR
2Group ,-OSiR
3 3Group ,-OAlR
4 2Group ,-NR
5 2Group ,-SiR
6 3Group or-N (R
7) AlR
8 2Group; N is 1 to 2; R
2, R
3, R
4And R
8Respectively do for oneself methyl, ethyl, sec.-propyl, isobutyl-, cyclohexyl, phenyl etc.; R
5Be hydrogen atom, methyl, ethyl, sec.-propyl, phenyl, trimethyl silyl etc.; R
6And R
7Each is methyl, ethyl etc. naturally.
The example of these organo-aluminium compounds comprises:
(1) chemical formula is R
1 nAl (OR
2)
3-nCompound, as methoxyl group dimethyl aluminium, oxyethyl group diethyl aluminum and methoxyl group diisobutyl aluminum;
(2) chemical formula is R
1 nAl (OSiR
3 3)
3-nCompound, as Et
2Al (OSiMe
3), (iso-Bu)
2Al (OSiMe
3) and (iso-Bu)
2Al (OSiEt
3);
(3) chemical formula is R
1 nAl (OAlR
4 2)
3-nCompound, as Et
2AlOAlEt
2(iso-Bu)
2AlOAl (iso-Bu)
2
(4) chemical formula is R
1 nAl (NR
5 2)
3-nCompound, as Me
2AlNEt
2, Et
2AlNHMe, Me
2AlNHEt, Et
2AlN (SiMe
3)
2(iso-Bu)
2AlN (SiMe
3)
2And
(5) chemical formula is R
1 nAl (SiR
6 3)
3-nCompound, as (iso-Bu)
2AlSiMe
3And
(6) chemical formula is R
1 nAl (N (R
7) AlR
8 2)
3-nCompound, as Et
2AlN (Me) AlEt
2(iso-Bu)
2AlN (Et) Al (iso-Bu)
2
In the organo-aluminium compound of chemical formula (i) and (ii) expression, be preferably chemical formula R
1 3Al, R
1 nAl (OR
2)
3-nAnd R
1 nAl (OAlR
4 2)
3-nCompound, the R that good especially is in the above-mentioned chemical formula
1Be that iso-alkyl, n are 2 compounds.
Olefin polymerization catalysis (Cat-1) is by component (a), component (b), and component (d) (if necessary) forms; Olefin polymerization catalysis (Cat-2) (solid catalyst (Cat-2)) is formed by solid catalyst (component), and wherein component (a) and component (b) load on the component (c), also has component (d) if necessary.
Fig. 1 shows the step of preparation olefin polymerization catalysis (Cat-1).
Can by in polymerization reactor inside or the outside catalyst component is contacted with each other prepare olefin polymerization catalysis (Cat-1).The component (a) of making solids fraction is in advance contacted with component (b) to form solid catalyst, component (a) is contacted with component (b) to form solid catalyst, then solid catalyst be added in people's polymerization reaction system.
Component (a), component (b) and component (d) (if necessary) are contacted, can form olefin polymerization catalysis (Cat-1).These catalyst components can contact with any order, but when component (a) and component (b) when contacting, preferably component (b) are joined in the suspension of component (a).Be preferably two or more transistion metal compounds of prior mixing (component (b-I) and (b-II)) and form component (b), contact with other component then.
The example that is used for preparing the inert hydrocarbon solvent of olefin polymerization catalysis (Cat-1) comprises aliphatic hydrocrbon, as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; Alicyclic hydrocarbon is as pentamethylene, hexanaphthene and methylcyclopentane; Aromatic hydrocarbons is as benzene, toluene and dimethylbenzene; Halon is as ethylene chloride, chlorobenzene and methylene dichloride; And the mixture of these hydrocarbon.
When the contacting of component (a), component (b) and component (d) (if necessary), the concentration of component (a) is preferably the 0.3-3 moles per litre of solvent in the scope of 0.1-5 moles per litre of solvent, in the aluminium in the component (a).The atomic ratio (Al/ transition metal) of the transition metal in aluminium (Al) in the component (a) and the component (b) is general in 10 to 500 scope, is preferably 20 to 200.The atomic ratio (Al-d/Al-a) that can choose the aluminium atom (Al-a) in aluminium atom (Al-d) and the component (a) in the component (d) of use wantonly is general in-0.02 to 3 scope, is preferably 0.05 to 1.5.When the contacting of component (a), component (b) and component (d) (if necessary), mixing temperature is usually in-50 to 150 ℃ scope, be preferably-20 to 120 ℃, in 1 minute to 50 hours scope, be preferably 10 minutes to 25 hours duration of contact usually.
In the olefin polymerization catalysis that as above makes (Cat-1), the content of the component (b) in the 1 gram catalyzer is preferably 5 * 10
-6To 5 * 10
-4Mole is preferably 10
-5To 2 * 10
-4Mole is in transition metal atoms; The component (a) in the 1 gram catalyzer and the total content of component (d) are preferably 10
-2To 2.5 * 10
-2Mole is preferably 1.5 * 10
-2To 2 * 10
-2Mole is in the aluminium atom.
Make carrier (c) load component (a), component (b) and component (d) (if necessary), prepare solid catalyst (Cat-2) thus.
Though can contacting with any order, component (a), component (b), carrier (c) and component (d) (if necessary) prepare solid catalyst (Cat-2), but the component of being preferably (a) contacts with carrier (c), contact with component (b) then, and then contact with component (d) (if necessary).Be preferably two or more transistion metal compounds of prior mixing (component (b-I) and (b-II)) and form component (b), contact with other component then.
Contact between component (a), component (b), carrier (c) and the component (d) is carried out in inert hydrocarbon solvent, be used to prepare the example of inert hydrocarbon solvent of catalyzer and the above-mentioned solvent phase that is used for preparing olefin polymerization catalysis (Cat-1) with.
During contact between component (a), component (b), carrier (c) and component (d) (if necessary), the consumption of component (b) is generally 5 * 10 in the 1 gram carrier (c)
-6To 5 * 10
-4Mole is preferably 10
-5To 2 * 10
-4Mole is in transition metal atoms; The concentration of component (b) is about 10
-4To 2 * 10
-2In the scope of moles per litre of solvent, be preferably 2 * 10
-4To 10
-2Moles per litre of solvent is in transition metal atoms.The atomic ratio (Al/ transition metal) of the transition metal in aluminium (Al) in the component (a) and the component (b) is general in 10 to 500 scope, is preferably 20 to 200.The atomic ratio (Al-d/Al-a) that can choose the aluminium atom (Al-a) in aluminium atom (Al-d) and the component (a) in the component (d) of use wantonly is general in 0.02 to 3 scope, is preferably 0.05 to 1.5.When the contacting of component (a), component (b), carrier (c) and component (d) (if necessary), mixing temperature is usually in-50 to 150 ℃ scope, be preferably-20 to 120 ℃, in 1 minute to 50 hours scope, be preferably 10 minutes to 25 hours duration of contact usually.
When the solid catalyst (Cat-2) of as above preparation, the amount of the component (b) of 1 gram catalyzer (c) institute load is preferably 5 * 10
-6To 5 * 10
-4Mole is preferably 10
-5To 2 * 10
-4Mole is in transition metal atoms; The component (a) of 1 gram carrier (c) institute load and the total content of component (d) are preferably 10
-3To 5 * 10
-2Mole is preferably 2 * 10
-3To 2 * 10
-2Mole is in the aluminium atom.
Olefin polymerization catalysis (Cat-2) can be the prepolymerized pre-polymerized catalyst of alkene wherein.
In the presence of component (a), component (b) and carrier (c), in inert hydrocarbon solvent, add alkene and carry out prepolymerization, prepare pre-polymerized catalyst.Be preferably, solid catalyst component (Cat-2) is formed by component (a), component (b) and carrier (c).Solid catalyst component (Cat-2) can also with component (a) and/or component (d) blend.
In order to prepare pre-polymerized catalyst, feasible is alkene to be added contain in the suspension of the solid catalyst (Cat-2) (solid catalyst component) that makes, perhaps feasible is separate solid catalyzer (Cat-2) from the suspension that contains the solid catalyst (Cat-2) that makes, then this solid catalyst is resuspended in the unreactive hydrocarbons, in the suspension of gained, adds alkene.
In the preparation of pre-polymerized catalyst, the consumption of component (b) is generally 10
-6To 2 * 10
-2Moles per litre of solvent is preferably 5 * 10
-5To 10
-2Moles per litre of solvent is in the transition metal atoms in the component (b); The consumption of component (b) is 5 * 10 in the 1 gram carrier (c)
-6To 5 * 10
-4Mole is preferably 10
-5To 2 * 10
-4Mole is in the transition metal atoms in the component (b).The atomic ratio (Al/ transition metal) of the transition metal in aluminium (Al) in the component (a) and the component (b) is general in 10 to 500 scope, is preferably 20 to 200.The atomic ratio (Al-d/Al-a) that can choose the aluminium atom (Al-a) in aluminium atom (Al-d) and the component (a) in the component (d) of use wantonly is general in 0.02 to 3 scope, is preferably 0.05 to 1.5.
The consumption of solid catalyst component is generally 10
-6To 2 * 10
-2Moles per litre of solvent is preferably 5 * 10
-5To 10
-2Moles per litre of solvent is in the transition metal in the transistion metal compound.
The prepolymerization temperature in-20 to 80 ℃ scope, is 0 to 60 ℃ usually preferably, and the prepolymerization time in 0.5 to 200 hour scope, is preferably 2 to 50 hours usually.
The example of used alkene comprises ethene in the prepolymerization; The alpha-olefin of 3 to 20 carbon atoms is as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecylene and tetradecene.Wherein, good especially is ethene, the perhaps combination of used identical alpha-olefin in ethene and the polyreaction.
Pre-polymerized catalyst prepares with for example following method.Carrier is suspended in obtains suspension in the inert hydrocarbon solvent.In this suspension, add Organoaluminoxy compound (component (a)), make their one given period of reaction.Remove supernatant liquid then, with gained solid resuspending in unreactive hydrocarbons.In this system, add transistion metal compound (component (b)), make their one given period of reaction.Remove supernatant liquid then and obtain the solid catalyst component.Subsequently, in the unreactive hydrocarbons that contain organo-aluminium compound (component (d)), add the solid catalyst component, add alkene again.Obtain pre-polymerized catalyst thus.
In prepolymerization, 1 gram carrier (c) should make the olefin polymer of 0.1 to 500 gram, is preferably 0.2 to 300 gram, is more preferably 0.5 to 200 gram.
In pre-polymerized catalyst, the amount of the component (b) of 1 gram carrier (c) institute load is preferably 5 * 10
-6To 5 * 10
-4Mole is preferably 10
-5To 2 * 10
-4Mole is in transition metal atoms; The component (a) of institute's load and the amount of component (d) be preferably make component (a) and (d) in aluminium atom (Al) and component (b) in the mol ratio (Al/M) of transition metal atoms (M) be 5 to 200, be preferably 10 to 150.
Prepolymerization can be carried out with in batch process and the continuous processing any, can or carry out under pressure at decompression, normal atmosphere.In pre-polymerization process, it is the prepolymer of 0.2 to 7dl/g (being preferably 0.5 to 5dl/g) that hydrogen is present in the system to make limiting viscosity (η) (recording in 135 ℃) in naphthane.
In the present invention, the copolymerization of ethene and alpha-olefin is that (being preferably in gas phase) carries out in the presence of above-mentioned olefin polymerization catalysis, in gas phase or slurry liquid phase.In slurry polymerization, as solvent, perhaps use alkene itself as solvent with unreactive hydrocarbons.
The example that is used for the inert hydrocarbon solvent of slurry polymerization comprises aliphatic hydrocrbon, as propane, butane, Trimethylmethane, pentane, hexane, octane, decane, dodecane, n-Hexadecane and octadecane; Alicyclic hydrocarbon is as pentamethylene, methylcyclopentane, hexanaphthene and cyclooctane; Aromatic hydrocarbons is as benzene, toluene and dimethylbenzene; Petroleum fractions is as gasoline, kerosene and gas oil.In inert hydrocarbon solvent, be preferably aliphatic hydrocrbon, alicyclic hydrocarbon and petroleum fractions.
When copolymerization was carried out with slurry polymerization or vapour phase polymerization, catalyst consumption was preferably 10 usually
-8To 10
-3Mol is preferably 10
-7To 10
-4Mol is with the densitometer of transition metal atoms in the polymerization reaction system.
By component (a), component (b) but and in the olefin polymerization catalysis that forms of optional components (d), aluminium atom (Al) in the component (d) to the atomic ratio (Al/M) of the transition metal atoms (M) in the transistion metal compound (b) in 5 to 300 scope, be preferably 10 to 200, be more preferably 15 to 150.
Use by component (a), component (b), carrier (c) but and the olefin polymerization catalysis that forms of optional components (d) carry out in the polyreaction, the Organoaluminoxy compound on loading on carrier (component (a)), can also use the Organoaluminoxy compound that does not load on the carrier.In this case, do not load on aluminium atom (Al) in the Organoaluminoxy compound on the carrier to the atomic ratio (Al/M) of the transition metal atoms (M) in the transistion metal compound (b) in 5 to 300 scope, be preferably 10 to 200, be more preferably 15 to 150.The component (d) that can choose use wantonly can load on the carrier (c).In polymerization process, can add component (d).Can also in polymerization process, add the component (d) that loads in advance on the carrier.The component (d) that has loaded on the carrier can be identical or different with the component (d) that adds in polymerization process.Can choose wantonly aluminium atom (Al) in the component (d) of use to the atomic ratio (Al/M) of the transition metal atoms (M) in the transistion metal compound (b) in 5 to 300 scope, be preferably 10 to 200, be more preferably 15 to 150.
When carrying out slurry polymerization in the present invention, polymerization temperature is generally-50 to 100 ℃, is preferably 0 to 90 ℃.When carrying out gas phase polymerization, polymerization temperature is generally 0 to 120 ℃, is preferably 20 to 100 ℃.
Polymerization pressure be generally normal atmosphere to double centner/centimetre
2, be preferably 2 to 50 kg/cm
2Polyreaction can be carried out with any of batch process, semi-continuous process and continuous processing.
Polyreaction can be used in the step of two under the differential responses condition or multistep is carried out.In the used olefin polymerization catalysis of the present invention, except said components, can also contain the component that other is used for olefinic polymerization.
Can comprise ethene with the example that this olefin polymerization catalysis carries out polymeric alkene; The above-mentioned alpha-olefin that contains 6 to 8 carbon atoms; Other alpha-olefin is as propylene, 1-butylene, 1-amylene, 4-methyl-1-pentene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene; The cycloolefin that contains 3 to 20 carbon atoms is as cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene, tetracyclododecane and 2-methyl isophthalic acid, 4,5,8-dimethylene-1,2,3,4,4a, 5,8,8a-octahydro naphthalene.Also can use vinylbenzene, vinyl cyclohexane and diene.
In the ethylene/alpha-olefin copolymer of the present invention that obtains with olefine polymerizing process, the unitary amount of component that is obtained by ethene is preferably 50-100% (weight), be preferably 55-99% (weight), be more preferably 65-98% (weight), best is 70-96% (weight), and the unitary amount of component that is obtained by the alpha-olefin that contains 6 to 8 carbon atoms is 0-50% (weight), is preferably 1-45% (weight), be more preferably 2-35% (weight), best is 4-30% (weight).
The ethylene/alpha-olefin copolymer that so obtains shows above-mentioned character (A-i) to (A-iii), so processability is good, and can make transparency and the good film of physical strength.
Ethylene copolymer composition (A ')
Ethylene copolymer composition (A ') has essentially identical content and purposes with ethylene/alpha-olefin copolymer (A), and it comprises (B) ethylene/alpha-olefin copolymer and (C) is different from the ethylene/alpha-olefin copolymer of multipolymer (B).
Ethylene/alpha-olefin copolymer (B) is the random copolymers of the alpha-olefin of ethene and 6 to 8 carbon atoms.The example of the alpha-olefin of 6 to 8 carbon atoms comprises alkene same as described above.
In ethylene/alpha-olefin copolymer (B), the unitary amount of component that is obtained by ethene is preferably 50-100% (weight), be preferably 55-99% (weight), be more preferably 65-98% (weight), best is 70-96% (weight), and the unitary amount of component that is obtained by the alpha-olefin of 6 to 8 carbon atoms is preferably 0-50% (weight), is preferably 1-45% (weight), be more preferably 2-35% (weight), best is 4-30% (weight).
Ethylene/alpha-olefin copolymer (B) is preferably has following character (B-i) to (B-vii), and good especially is to have following character (B-i) to (B-viii).
(B-i) density (d) is at the 0.880-0.970 gram per centimeter
3Scope in, be the 0.880-0.960 gram per centimeter preferably
3, better be the 0.890-0.935 gram per centimeter
3, best is the 0.905-0.930 gram per centimeter
3
(B-ii) melt flow rate (MFR) (MFR) is preferably 0.05 to 50 gram/10 minutes in/10 minutes scope of 0.02-200 gram, is more preferably 0.1 to 10 gram/10 minutes.
(B-iii) be dissolved in the component mark (W (% weight)) and the density (d (gram per centimeter of decane 23 ℃ the time
3)) satisfy following the relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1,
Be preferably W＜60 * exp (100 (d-0.88))+0.1,
Be more preferably W＜40 * exp (100 (d-0.88))+0.1,
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.26* exp (100 (d-0.88))+0.1.
The temperature of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) (Tm (℃)) and density (d (gram per centimeter (B-iv)
3)) satisfy following the relation:
Tm＜400×d-248，
Be preferably Tm＜450 * d-296,
Be more preferably Tm＜500 * d-343,
That good especially is Tm＜550 * d-392.
The ethylene/alpha-olefin copolymer (B) that has the relation that is defined as above between component mark (W) that has the relation that is defined as above and be dissolved in n-decane between the temperature (Tm) of the endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and the density (d) and density (d) has narrow component and distributes.
(B-v) melt tension (MT (gram)) and melt flow rate (MFR) (MFR (restraining/10 minutes)) satisfy following relation:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
Be preferably 9.0 * MFR
-0.65＞MT＞2.3 * MFR
-0.84,
Be more preferably 8.5 * MFR
-0.65＞MT＞2.5 * MFR
-0.84
Ethylene/alpha-olefin copolymer with above character shows high melt tension (MT), so have good formability.
(B-vi) flow-activation energy ((Ea) * 10 of determining by the synergetic shift factor of the time-temperature of flow curve
-4J/molK), relation below the content of alpha-olefin (x% mole) satisfies in carbonatoms of alpha-olefin (C) and the multipolymer in the multipolymer: (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1660) * x+2.87
Be preferably (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1500) * x+2.87
Be more preferably (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1300) * x+2.87
(B-vii) molecular weight distribution (M that records by GPC
w/ M
n, M
w: weight-average molecular weight, M
n: number-average molecular weight) meet the following conditions:
2.2＜M
w/M
n＜3.5，
Be preferably 2.4＜M
w/ M
n＜3.0.
Molecular weight distribution (M
w/ M
n) use the GPC-150C of Milipore Co. manufacturing to measure with the following method.
Using diameter is that 72 millimeters, length are 600 millimeters TSK-GNH-HT post, and column temperature is 140 ℃.In post, with orthodichlorobenzene (available from Wako Junyaku Kogyo K.K.) as moving phase, with the BHT of 0.025% (weight) (available from Takeda Chemical Industries, Ltd.), the sample (concentration is 0.1% (weight)) of 500 microlitres is flowed as oxidation inhibitor.With differential refractometer as detector.Use Mw＜1,000 and Mw＞4 * 10 available from TOHSO K.K.
6Polystyrene and available from 1,000＜Mw≤4 * 10 of Pressure Chemical Co.
6Polystyrene as polystyrene standard.
(B-viii) number of the unsaturated link(age) that exists in the copolymer molecule is no more than 0.5 with 1,000 carbon atom meter, and is lower than 1 in 1 copolymer molecule.
The following quantitative assay of carrying out unsaturated link(age): use
13C-NMR seeks the areal intensity (area intensity) of the signal (i.e. signal in 10 to the 50ppm scopes) do not belong to two keys and belongs to the areal intensity of the signal (i.e. signal in 105 to the 150ppm scopes) of pair keys from integrated curve, calculates the ratio between these intensity.
Can be in the presence of olefin polymerization catalysis, the alpha-olefin of ethene and 6 to 8 carbon atoms is carried out copolymerization, obtain ethylene/alpha-olefin copolymer (B), described catalyzer for example comprises, (a) Organoaluminoxy compound and the transistion metal compound of (b-II) being represented by above-mentioned chemical formula (II).Identical in Organoaluminoxy compound (a) and transistion metal compound (b-II) and the above-mentioned method for preparing ethylene/alpha-olefin copolymer (A).Be similar to preparation ethylene/alpha-olefin copolymer (A), also can use carrier (c) and organo-aluminium compound (d), can carry out the prepolymerization reaction.Identical in amounts of components, prepolymerization reaction conditions and the polymeric reaction condition that is used for preparing ethylene/alpha-olefin copolymer (B) and the preparation ethylene/alpha-olefin copolymer (A).
Ethylene/alpha-olefin copolymer (C) is the random copolymers of the alpha-olefin of ethene and 6 to 8 carbon atoms.The example of the alpha-olefin of 6 to 8 carbon atoms comprises alkene same as described above.
In the used ethylene/alpha-olefin copolymer of the present invention (C), requirement is 50-100% (weight), is preferably 55-99% (weight) by the unitary amount of component that ethene obtains, be more preferably 65-98% (weight), best is 70-96% (weight), the unitary amount of component that is obtained by the alpha-olefin that contains 6 to 8 carbon atoms is 0-50% (weight), be preferably 1-45% (weight), be more preferably 2-35% (weight), good especially is 4-30% (weight).
Ethylene/alpha-olefin copolymer (C) is preferably has following character (C-i) to (C-v), and good especially is to have following character (C-i) to (C-vi):
(C-i) density (d) is at the 0.880-0.970 gram per centimeter
3Scope in, be the 0.880-0.960 gram per centimeter preferably
3, better be the 0.890-0.935 gram per centimeter
3, best is the 0.905-0.930 gram per centimeter
3
(C-ii) melt flow rate (MFR) (MFR) is preferably 0.05 to 50 gram/10 minutes in/10 minutes scope of 0.02-200 gram, is more preferably 0.1 to 10 gram/10 minutes.
(C-iii) be dissolved in the component mark (W (% weight)) and the density (d (gram per centimeter of decane 23 ℃ the time
3)) satisfy following the relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1,
Be preferably W＜60 * exp (100 (d-0.88))+0.1,
Be more preferably W＜40 * exp (100 (d-0.88))+0.1,
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.25* exp (100 (d-0.88))+0.1.
The temperature of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) (Tm (℃)) and density (d (gram per centimeter (C-iv)
3)) satisfy following the relation:
Tm＜400×d-248，
Be preferably Tm＜450 * d-296,
Be more preferably Tm＜500 * d-343,
That good especially is Tm＜550 * d-392.
The ethylene/alpha-olefin copolymer (C) that has the relation that is defined as above between component mark (W) that has the relation that is defined as above and be dissolved in n-decane between the temperature (Tm) of the endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and the density (d) and density (d) has narrow component and distributes.
(C-v) melt tension (MT (gram)) and melt flow rate (MFR) (MFR (restraining/10 minutes)) satisfy following relation:
MT≤2.2×MFR
-0.84。
(C-vi) number of the unsaturated link(age) that exists in the copolymer molecule is no more than 0.5 with 1,000 carbon atom meter, and is lower than 1 in 1 copolymer molecule.
Can be in the presence of olefin polymerization catalysis, the alpha-olefin of ethene and 6 to 8 carbon atoms is carried out copolymerization, obtain ethylene/alpha-olefin copolymer (C), described catalyzer for example comprises, (a) Organoaluminoxy compound and the transistion metal compound of (b-I) being represented by above-mentioned chemical formula (I).Identical in Organoaluminoxy compound (a) and transistion metal compound (b-I) and the above-mentioned method for preparing ethylene/alpha-olefin copolymer (A).Be similar to preparation ethylene/alpha-olefin copolymer (A), also can use carrier (c) and organo-aluminium compound (d), can carry out the prepolymerization reaction.Identical in amounts of components, prepolymerization reaction conditions and the polymeric reaction condition that is used for preparing ethylene/alpha-olefin copolymer (C) and the preparation ethylene/alpha-olefin copolymer (A).
In ethylene copolymer composition of the present invention (A '), requiring the content of ethylene/alpha-olefin copolymer (B) is 1-90% (weight), be preferably 2-80% (weight), the content of ethylene/alpha-olefin copolymer (C) is 10-99% (weight), is preferably 20-98% (weight).
In the ethylene copolymer composition (A ') that comprises ethylene/alpha-olefin copolymer (B) and ethylene/alpha-olefin copolymer (C), the melt flow rate (MFR) of ethylene/alpha-olefin copolymer (C) (MFR (C)) meets the following conditions with the ratio of the melt flow rate (MFR) (MFR (B)) of ethylene/alpha-olefin copolymer (B):
1＜(MFR(C))/(MFR(B))≤20。
In ethylene copolymer composition (A '), ethylene/alpha-olefin copolymer (B) and (C) all be preferably ethene/1-hexene copolymer.In this case, as described below, ethylene copolymer composition (A ') has essentially identical character with ethylene/alpha-olefin copolymer (A), can expect that it has and the identical purposes of multipolymer (A).
(A '-i) melt tension (MT (gram)) and melt flow rate (MFR) (MFR (restraining/10 minutes)) satisfy following relation:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
Be preferably 9.0 * MFR
-0.65＞MT＞2.3 * MFR
-0.84,
Be more preferably 8.5 * MFR
-0.65＞MT＞2.5 * MFR
-0.84
Have above character ethylene copolymer composition (A ') thus the melt tension height have good processability.
(A '-ii) by definite flow-activation energy ((Ea) * 10 of the synergetic shift factor of the time-temperature of flow curve
-4J/molK), multipolymer (B) and (C) in the carbonatoms (C) of 1-hexene and multipolymer (B) and (C) in the total content (x% mole) of 1-hexene concern below satisfying: (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1660) * x+2.87
Be preferably (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1500) * x+2.87
Be more preferably (0.039 Ln (C-2)+0.0096) * x+2.87＜(Ea) * 10
-4≤ (0.039 Ln (C-2)+0.1300) * x+2.87
(A '-mist degree of the film of 30 micron thickness that iii) made with blow moulding by ethylene copolymer composition (A ') meets the following conditions:
Flow index (FI) (is defined as in the time of 190 ℃ when shear-stress and reaches 2.4 * 10
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI 〉=100 * MFR,
Mist degree＜0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
And
Flow index (FI) (is defined as in the time of 190 ℃ when shear-stress and reaches 2.4 * 10
6Dynes per centimeter
2The time given shearing rate) and melt flow rate (MFR) (MFR) satisfy and concern under the situation of FI＜100 * MFR,
Mist degree＜0.25/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
Wherein, d represents density (gram per centimeter
3), MT represents melt tension (gram), C represents the carbon atom number of 1-hexene, and promptly 6.
The ethylene copolymer composition (A ') that satisfies above condition has good processability, can make the good film of transparency.
Ethylene copolymer composition of the present invention (A ') is preferably except above character, also has following character:
(A '-molecular weight distribution (M that iv) records by GPC
w/ M
n, M
w: weight-average molecular weight, M
n: number-average molecular weight) meet the following conditions:
2.0≤M
w/M
n≤2.5，
Be preferably 2.0≤M
w/ M
n≤ 2.4.
In ethylene copolymer composition of the present invention (A '), the unitary amount of component that requirement is obtained by ethene is 50-100% (weight), be preferably 55-99% (weight), be more preferably 65-98% (weight), best is 70-96% (weight), and the unitary amount of component that is obtained by the alpha-olefin (being preferably the 1-hexene) of 6 to 8 carbon atoms is 0-50% (weight), is preferably 1-45% (weight), be more preferably 2-35% (weight), best is 4-30% (weight).
The density (d) of ethylene copolymer composition (A ') is preferably the 0.880-0.970 gram per centimeter
3, be preferably the 0.880-0.960 gram per centimeter
3, be more preferably the 0.890-0.935 gram per centimeter
3, best is the 0.905-0.930 gram per centimeter
3
The melt flow rate (MFR) (MFR) of ethylene copolymer composition (A ') is preferably 0.05-200 gram/10 minutes, is preferably 0.08-50 gram/10 minutes, is more preferably 0.1-10 gram/10 minutes.
Be dissolved in component mark (W (weight %)) and its density (d (gram per centimeter of n-decane in the ethylene copolymer composition in the time of 23 ℃ (A ')
3) satisfy following the relation:
Under MFR≤situation of/10 minutes of 10 grams,
W＜80×exp(-100(d-0.88))+0.1，
Be preferably W＜60 * exp (100 (d-0.88))+0.1,
Be more preferably W＜40 * exp (100 (d-0.88))+0.1,
Under MFR＞situation of/10 minutes of 10 grams,
W＜80×(MFR-9)
0.26×exp(-100(d-0.88))+0.1
The temperature of ethylene copolymer composition (A ') the endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) (Tm (℃)) and density (d (gram per centimeter
3)) satisfy following the relation:
Tm＜400×d-248，
Be preferably Tm＜450 * d-296,
Be more preferably Tm＜500 * d-343,
That good especially is Tm＜550 * d-392.
The ethylene copolymer composition (A ') that has the relation that is defined as above between component mark (W) that has the relation that is defined as above and be dissolved in n-decane between the temperature (Tm) of the endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and the density (d) and density (d) has narrow component and distributes.
The ethylene copolymer composition (A ') that comprises ethylene/alpha-olefin copolymer (B) and ethylene/alpha-olefin copolymer (C) can prepare with ordinary method, for example following method:
(1) with mechanically mixing or melting mixing ethylene/alpha-olefin copolymer (B), ethylene/alpha-olefin copolymers (C) such as rotary drum, extrusion machine, kneaders with can choose other component of adding wantonly.
(2) with ethylene/alpha-olefin copolymer (B), ethylene/alpha-olefin copolymer (C) and other components dissolved that can choose adding wantonly at suitable good solvent (as varsol, as hexane, heptane, decane, hexanaphthene, benzene, toluene and dimethylbenzene) in, remove from solution then and desolvate.
(3) ethylene/alpha-olefin copolymer (B), ethylene/alpha-olefin copolymer (C) and other component that can choose adding wantonly are dissolved in respectively in the good solvent, these solution are mixed, from mixture, remove and desolvate.
(4) method (1) to (3) is suitably made up.
Ethylene/alpha-olefin copolymer of the invention described above (A) and ethylene copolymer composition (A ') all have good formability, can make the good film of transparency and physical strength.Yet they can make up with other polymkeric substance (being preferably ethylene/alpha-olefin copolymer).As ethylene/alpha-olefin copolymer, the good especially following ethylene/alpha-olefin copolymer (D) that is to use.
Ethylene/alpha-olefin copolymer (D) is the random copolymers of the alpha-olefin of ethene and 3 to 20 carbon atoms.The example of the alpha-olefin of 3 to 20 carbon atoms comprises propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene.
In ethylene/alpha-olefin copolymer (D), the unitary amount of component that requirement is obtained by ethene is 50-100% (weight), be preferably 55-99% (weight), be more preferably 65-98% (weight), best is 70-96% (weight), and the unitary amount of component that is obtained by the alpha-olefin of 3 to 20 carbon atoms is 0-50% (weight), is preferably 1-45% (weight), be more preferably 2-35% (weight), best is 4-30% (weight).
Ethylene/alpha-olefin copolymer (D) is preferably has following character (D-i) to (D-ii), and good especially is to have following character (D-i) to (D-iv).
(D-i) density (d) is at the 0.850-0.980 gram per centimeter
3Scope in, be the 0.910-0.960 gram per centimeter preferably
3, better be the 0.915-0.955 gram per centimeter
3, best is the 0.920-0.950 gram per centimeter
3
(D-ii) limiting viscosity (η) that records in naphthane 135 ℃ the time is 0.4-1.25dl/g in the scope of 0.4-8 dl/g preferably, better is 0.5-1.23dl/g.
The temperature of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) (Tm (℃)) and density (d (gram per centimeter (D-iii)
3)) satisfy following the relation:
Tm＜400×d-250，
Be preferably Tm＜450 * d-297,
Be more preferably Tm＜500 * d-344,
That good especially is Tm＜550 * d-391.
(D-iv) be dissolved in the component mark (W (% weight)) and the density (d (gram per centimeter of n-decane during room temperature
3)) satisfy following the relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1,
Be preferably W＜60 * exp (100 (d-0.88))+0.1,
Be more preferably W＜40 * exp (100 (d-0.88))+0.1,
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.26* exp (100 (d-0.88))+0.1.
The ethylene/alpha-olefin copolymer (D) that has the relation that is defined as above between component mark (W) that has the relation that is defined as above and be dissolved in n-decane between the temperature (Tm) of the endothermic curve maximum peak position that records with differential scanning calorimeter (DSC) and the density (d) and density (d) has narrow component and distributes.
Ethylene/alpha-olefin copolymer (A) is different from ethylene/alpha-olefin copolymer (D); Ethylene/alpha-olefin copolymer (B) and (C) all be different from ethylene/alpha-olefin copolymer (D).Particularly, can ethylene/alpha-olefin copolymer (D) and ethylene/alpha-olefin copolymer (A) to (C) difference be come from following character.
What multipolymer (D) was different from multipolymer (A) is that multipolymer (D) does not satisfy at least one in the required character of multipolymer (A) (A-i) to (A-iii).What multipolymer (B) was different from multipolymer (D) is that multipolymer (D) does not satisfy at least one in multipolymer (B) character (B-iii) to (B-vii).In addition, multipolymer (D) does not satisfy at least one in the required character of multipolymer (C) (C-iii) to (C-v).
Can be in the presence of olefin polymerization catalysis the alpha-olefin of ethene and 3 to 20 carbon atoms be carried out copolymerization and prepare ethylene/alpha-olefin copolymer (D), described olefin polymerization catalysis for example comprises (a) Organoaluminoxy compound and (b-III) transistion metal compound of following chemical formula (III) expression.Identical in Organoaluminoxy compound (a) and aforementioned preparation ethylene/alpha-olefin copolymer (A) method.Be similar to preparation ethylene/alpha-olefin copolymer (A), can use carrier (c) and organo-aluminium compound (d), can carry out the prepolymerization reaction.Identical in amounts of components, prepolymerization reaction conditions and polymeric reaction condition and the preparation ethylene/alpha-olefin copolymer (A) of preparation ethylene/alpha-olefin copolymer (D).
(b-III) is as described below for transistion metal compound.
(b-III) transistion metal compound
The transistion metal compound (b-III) (hereinafter being sometimes referred to as " component (b-III) ") that is used for preparing ethylene/alpha-olefin copolymer (D) is the compound that contains periodictable the 4th group 4 transition metal of the ligand with cyclopentadienyi skeleton.Any compound all can be used as transistion metal compound (b-III) and without particular limitation, and needing only it is the compound that contains periodictable the 4th group 4 transition metal of the ligand with cyclopentadienyi skeleton.Yet transistion metal compound (b-III) is preferably the compound of chemical formula (III) expression:
ML
3 x (III)
In chemical formula (III), M is the transition metal atoms that is selected from periodictable the 4th family, and concrete is zirconium, titanium or hafnium, is preferably zirconium.
X is the valency of transition metal.
L
3Be and transition metal atoms M coordinate ligand, at least one ligand L
3It is ligand with cyclopentadienyi skeleton.Example with ligand of cyclopentadienyi skeleton comprises, cyclopentadienyl; The cyclopentadienyl that alkyl replaces is as methyl cyclopentadienyl, dimethyl cyclopentadienyl, trimethylammonium cyclopentadienyl, tetramethyl-ring pentadienyl, pentamethyl-cyclopentadienyl, ethyl cyclopentadienyl, methylethyl cyclopentadienyl, propyl group cyclopentadienyl, methyl-propyl cyclopentadienyl, butyl cyclopentadienyl, methyl butyl cyclopentadienyl and hexyl cyclopentadienyl; Indenyl; 4,5,6, the 7-tetrahydro indenyl; And fluorenyl.These groups can be by replacements such as halogen atom, trialkylsilkls.
Have in the ligand of cyclopentadienyi skeleton, good especially is the cyclopentadienyl that alkyl replaces.
When the compound of chemical formula (III) expression contained two or more ligand with cyclopentadienyi skeleton, two in them can be passed through the following groups bonding, and these groups such as alkylidene group are as ethylidene or propylidene; The alkylidene group that alkyl replaces is as isopropylidene or phenylbenzene methylene radical; Silylene; Or the silylene that replaces,, phenylbenzene silylene silica-based or aminomethyl phenyl silylene as dimethylated methylene.
In chemical formula (III), the L except that ligand with cyclopentadienyi skeleton
3Be alkyl, alkoxyl group, aryloxy, trialkylsilkl, halogen atom or the hydrogen atom that contains 1 to 12 carbon atom, each in them all with chemical formula (I) in L
1Pointed group or atom are identical, or SO
3R group (R is the alkyl of 1 to 8 carbon atom, and it can have substituting group, as halogen).By SO
3The example of the ligand that R represents comprises tosic acid root (p-toluenesulfonato group), methanesulfonate and trifluoromethanesulfonic acid root.
Wherein the transition metal compound valency is that the transistion metal compound of for example 4 chemical formula (III) is more particularly represented by following chemical formula (III '):
R
2 kR
3 1R
4 mR
5 nM (III′)
Wherein, M is a transition metal atoms same as described above; R
2Be group (ligand) with cyclopentadienyi skeleton, R
3, R
4And R
5Group, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, aryloxy, triamino silyl, SO that each has cyclopentadienyi skeleton naturally
3R base, halogen atom or hydrogen atom; K is l or bigger integer; K+l+m+n=4.
Be preferably the use metallocene compound in the present invention, wherein R
3, R
4And R
5In one be group (ligand) with cyclopentadienyi skeleton, R wherein for example
2And R
3Each has the metallocene compound of the group (ligand) of cyclopentadienyi skeleton naturally.Group with cyclopentadienyi skeleton can come bonding by following groups, and these groups such as alkylidene group are as ethylidene or propylidene; The alkylidene group that alkyl replaces is as isopropylidene or phenylbenzene methylene radical; Silylene; Or the silylene that replaces,, phenylbenzene silylene silica-based or aminomethyl phenyl silylene as dimethylated methylene.In this case, other ligand is (as R
4And R
5) each has group, alkyl, cycloalkyl, aryl, aralkyl, alkoxyl group, aryloxy, trialkylsilkl, the SO of cyclopentadienyl naturally
3R base, halogen atom or hydrogen atom.
Example by the transistion metal compound of chemical formula (III) expression comprises:
Dichloride two (indenyl) close zirconium,
Dibrominated two (indenyl) close zirconium,
Two (tosic acid roots) two (indenyl) close zirconium,
Dichloride two (4,5,6, the 7-tetrahydro indenyl) close zirconium,
Dichloride two (fluorenyl) close zirconium,
Dichloride ethylene (indenyl) close zirconium,
Dibrominated ethylene (indenyl) close zirconium,
Ethylene (indenyl) dimethyl close zirconium,
Ethylene (indenyl) phenylbenzene close zirconium,
Monochlor(in)ate ethylene (indenyl) methyl close zirconium,
Two (methanesulfonate) ethylene (indenyl) closes zirconium
Two (tosic acid root) ethylenes (indenyl) close zirconium,
Two (trifluoromethanesulfonic acid root) ethylenes (indenyl) close zirconium,
Dichloride ethylene (4,5,6, the 7-tetrahydro indenyl) close zirconium,
Dichloride isopropylidene (cyclopentadienyl-fluorenyl) close zirconium,
Dichloride isopropylidene (cyclopentadienyl-methyl cyclopentadienyl) close zirconium,
Silica-based two (cyclopentadienyls) of dichloride dimethylated methylene close zirconium,
Silica-based two (methyl cyclopentadienyls) of dichloride dimethylated methylene close zirconium,
Silica-based two (the dimethyl cyclopentadienyls) of dichloride dimethylated methylene close zirconium,
Silica-based two (the trimethylammonium cyclopentadienyls) of dichloride dimethylated methylene close zirconium,
Silica-based two (indenyls) of dichloride dimethylated methylene close zirconium,
Silica-based two (indenyls) two of dimethylated methylene (trifluoromethanesulfonic acid root) close zirconium,
Dichloride dimethylated methylene silica-based (4,5,6, the 7-tetrahydro indenyl) close zirconium,
Dichloride dimethylated methylene silica-based (cyclopentadienyl-fluorenyl) close zirconium,
Dichloride phenylbenzene silylene two (indenyl) close zirconium,
Dichloride aminomethyl phenyl silylene two (indenyl) close zirconium,
Dichloride two (cyclopentadienyl) close zirconium,
Dibrominated two (cyclopentadienyl) close zirconium,
Monochlor(in)ate two (cyclopentadienyl) methyl close zirconium,
Monochlor(in)ate two (cyclopentadienyl) ethyl close zirconium,
Monochlor(in)ate two (cyclopentadienyl) cyclohexyl close zirconium,
Monochlor(in)ate two (cyclopentadienyl) phenyl close zirconium,
Monochlor(in)ate two (cyclopentadienyl) benzyl close zirconium,
One hydrogenation monochlor(in)ate two (cyclopentadienyl) close zirconium,
One hydrogenation two (cyclopentadienyl) methyl close zirconium,
Two (cyclopentadienyl) dimethyl close zirconium,
Two (cyclopentadienyl) phenylbenzene close zirconium,
Two (cyclopentadienyl) dibenzyl close zirconium,
Chlorination methoxyl group two (cyclopentadienyl) close zirconium,
Chlorination oxyethyl group two (cyclopentadienyl) close zirconium,
Two (cyclopentadienyls) two (methanesulfonate) close zirconium,
Two (cyclopentadienyls) two (tosic acid root) close zirconium,
Two (cyclopentadienyls) two (trifluoromethanesulfonic acid root) close zirconium,
Dichloride two (methyl cyclopentadienyl) close zirconium,
Dichloride two (dimethyl cyclopentadienyl) close zirconium,
Chlorination oxyethyl group two (dimethyl cyclopentadienyl) close zirconium,
Two (dimethyl cyclopentadienyls) two (trifluoromethanesulfonic acid root) close zirconium,
Dichloride two (ethyl cyclopentadienyl) close zirconium,
Dichloride two (methylethyl cyclopentadienyl) close zirconium,
Dichloride two (propyl group cyclopentadienyl) close zirconium,
Dichloride two (methyl-propyl cyclopentadienyl) close zirconium,
Dichloride two (butyl cyclopentadienyl) close zirconium,
Dichloride two (methyl butyl cyclopentadienyl) close zirconium,
Two (methyl butyl cyclopentadienyls) two (methanesulfonate) close zirconium,
Dichloride two (trimethylammonium cyclopentadienyl) close zirconium,
Dichloride two (tetramethyl-ring pentadienyl) close zirconium,
Dichloride two (pentamethyl-cyclopentadienyl) close zirconium,
Dichloride two (hexyl cyclopentadienyl) close zirconium and
Dichloride two (trimethyl silyl cyclopentadienyl) is closed zirconium.
In above these examples, dibasic cyclopentadienyl rings comprises 1,2-and 1, and the cyclopentadienyl rings that 3-replaces, trisubstituted cyclopentadienyl rings comprises 1,2,3-and 1,2, the cyclopentadienyl rings that 4-replaces.Alkyl (as propyl group and butyl) comprises isomer, as positive alkyl, iso-alkyl, secondary alkyl and tertiary alkyl.
Also spendable is the compound that the zirconium in the above-mentioned zirconium compounds of enumerating is replaced with titanium or hafnium.
The transistion metal compound of chemical formula (III) expression comprises the transistion metal compound (b-I) of chemical formula (I) expression and the transistion metal compound (b-II) of chemical formula (II) expression.
Alpha-olefin to ethene and 3 to 20 carbon atoms in the presence of above-mentioned olefin polymerization catalysis carries out copolymerization, can prepare ethylene/alpha-olefin copolymer (D), and the reaction mode of carrying out makes that the density of gained multipolymer is the 0.850-0.980 gram per centimeter
3
The consumption of ethylene/alpha-olefin copolymer (D) is preferably the 99-60 weight part, is more preferably the 95-60 weight part, in 100 parts by weight of ethylene/alpha-olefin copolymer (A) or ethylene copolymer composition (A ').
The composition that comprises ethylene/alpha-olefin copolymer (D) and ethylene/alpha-olefin copolymer (A) or ethylene copolymer composition (A ') can be prepared by above-mentioned ordinary method.Composition can be prepared with the multistep polymerization method, wherein copolymerization use one or more polymerization reactors, under different reaction conditionss, with two the step or multistep carry out.
Though ethylene/alpha-olefin copolymer of the present invention (A) and ethylene copolymer composition (A ') all can use in the various fields that conventional ethylene copolymer has been used so far and not have special restriction, yet they especially are fit to be used for preparing film (as casting film and blown film) and sheet material (as extruded sheet).These films can wait and make with common air cooling blow moulding, two step of air cooling blow moulding, high speed blow moulding, the T pattern head method of forming, water cooling blow moulding.The film that so makes has good transparency and physical strength, shows heat seal, thermal viscosity, thermotolerance and good adhesion tendency (blocking tendency), and these all are the characteristics of conventional LLDPE.And these films do not have surface viscosity, distribute because ethylene/alpha-olefin copolymer or ethylene copolymer composition show very narrow composition.In addition, multipolymer (A) and composition (A ') have good bubble stability when carrying out blowing, because their melt tension height.
The film that obtains by moulding ethylene/alpha-olefin copolymer (A) and ethylene copolymer composition (A ') suitable film and plastic film for agricultural use as various packing bags (as stdn bag, sugar bag or be used for the sack of oiliness or fluent meterial).These films can use with the form of multilayer film, and multilayer film is by obtaining film lamination on ground (as nylon, polyester etc.).
The method that is used for preparing ethylene/alpha-olefin copolymer of the present invention comprises: in the presence of olefin polymerization catalysis, alpha-olefin to ethene and 6 to 8 carbon atoms carries out copolymerization, described catalyzer comprises (a) Organoaluminoxy compound, (b-I) transistion metal compound and (b-II) transistion metal compound.In the method for the invention, also can use carrier (c) and organo-aluminium compound (d), can carry out prepolymerization, these are similar to the above-mentioned method for preparing ethylene/alpha-olefin copolymer (A).Identical in the inventive method component utilized consumption, prepolymerization reaction conditions and polymeric reaction condition and the preparation ethylene/alpha-olefin copolymer (A).
Ethylene/alpha-olefin copolymer of the present invention and ethylene copolymer composition have high melt tension and good formability.Can make transparency and the good film of physical strength by these ethylene/alpha-olefin copolymers and ethylene copolymer composition.
The present invention is further illustrated with reference to following examples, but should be appreciated that the present invention is not subjected to the restriction of these embodiment.
In an embodiment, in order to descend the performance of method evaluated for film.
Mist degree
Measure mist degree according to method ASTM D-1003-61.
Glossiness
Measure glossiness according to method JIS Z8741.
Dart impact strength
Carry out the measurement of dart impact strength with the A method among the ASTM D-1709.
Preparation embodiment 1
The preparation catalyst component
5.0 kilograms have been suspended in 80 liters of toluene in 10 hours silicon-dioxide of 250 ℃ of dryings, suspension has been cooled to 0 ℃.In suspension, drip the toluene solution (Al:1.33 mol) of 28.7 liters of methylaluminoxane, continue 1 hour.During dripping, the temperature of system is remained on 0 ℃.Subsequently, be reflected at and carried out under 0 ℃ 30 minutes, then system temperature is risen to 95 ℃ with time of 1.5 hours, under this temperature, reacted 20 hours.After this, system temperature is reduced to 60 ℃, decantation is removed supernatant liquid.
With gained solid toluene wash twice, and then be suspended in 80 liters of toluene.In system, drip 20.0 liters of dichloride two (methyl cyclopentadienyl) in 80 ℃ and close the toluene solution of zirconium (Zr:14.0 mmole/liter), continue 30 minutes, further reacted 2 hours at 80 ℃.Then, remove supernatant liquid,, obtain solid catalyst, contain 3.6 milligrams of zirconiums in per 1 gram solid catalyst with hexane wash residuum twice.
The preparation pre-polymerized catalyst
In 85 liters of hexanes that contain 1.7 moles of triisobutyl aluminiums, add 0.85 kilogram of solid catalyst that as above obtains of people and 77 gram 1-hexanes, carrying out the prepolymerization of ethene under 35 ℃ reacted 3.5 hours, obtain pre-polymerized catalyst, contain polyethylene 3 grams in per 1 gram solid catalyst.
Polymerization
In the fluidized bed gas-phase polymerization reactor of successive type, carry out the copolymerization of ethene and 1-hexene, polymerization temperature is that 80 ℃, total pressure are 20kg/cm
2-G.In system with zirconium atom count 0.05 mmole/hour the pre-polymerized catalyst that as above obtains of the continuous adding of speed and with 10 mmoles/hour speed add triisobutyl aluminium.In polymerization process, feed ethene, 1-hexene, hydrogen and nitrogen continuously to keep the gas phase composition constant.(gas phase is formed: 1-hexene/ethene=0.020, hydrogen/ethene=9.5 * 10
-4, ethylene concentration=50%).The productive rate of polymkeric substance is 4.1 kilograms/hour.Ethylene/alpha-olefin copolymer (B-1) melt kneading and granulation with gained.The melt property of multipolymer (B-1) and other character are as shown in table 1.
Preparation embodiment 2
The preparation catalyst component
With prepare " prepare catalyst component " among the embodiment 1 in identical method prepare the solid catalyst component, the toluene solution (Zr:34.0 mmole/liter) that different is closes zirconium with 8.2 liters of dichloride two (1,3-normal-butyl methyl cyclopentadienyl) replaces 20.0 liters of dichloride two (methyl cyclopentadienyl) to close the toluene solution of zirconium (Zr:14.0 mmole/liter).
The preparation pre-polymerized catalyst
Obtain pre-polymerized catalyst with preparation method identical among the embodiment 1, the solid catalyst component that obtains in different being to use above-mentioned " preparation catalyst component ".
Polymerization
Obtain ethylene copolymer (C-1) with preparation method identical among the embodiment 1, the pre-polymerized catalyst that obtains in different being to use above-mentioned " preparation pre-polymerized catalyst ", gas composition becomes: 1-hexene/ethene=0.020, hydrogen/ethene=5.0 * 10
-4, ethylene concentration=50%.The character of ethylene copolymer (C-1) is as shown in table 1.
Embodiment 1
The preparation catalyst component
With prepare " prepare catalyst component " among the embodiment 1 in identical method prepare the solid catalyst component, different is closes the toluene solution (Zr:34.0 mmole/liter) of zirconium and the toluene solution that 6.0 liters of dichloride two (methyl cyclopentadienyl) are closed zirconium (Zr:14.0 mmole/liter) with 5.8 liters of dichloride two (1,3-normal-butyl methyl cyclopentadienyl) and replaces 20.0 liters of dichloride two (methyl cyclopentadienyl) to close the toluene solution of zirconium (Zr:14.0 mmole/liter).
The preparation pre-polymerized catalyst
Obtain pre-polymerized catalyst with preparation method identical among the embodiment 1, the solid catalyst component that obtains in different being to use above-mentioned " preparation catalyst component ".
Polymerization
Obtain ethylene copolymer (A-1) with preparation method identical among the embodiment 1, the pre-polymerized catalyst that obtains in different being to use above-mentioned " preparation pre-polymerized catalyst ", gas composition becomes: 1-hexene/ethene=0.020, hydrogen/ethene=4.5 * 10
-4, ethylene concentration=50%.The character of ethylene copolymer (A-1) is as shown in table 1.
Embodiment 2
Polymerization
Obtain ethylene/alpha-olefin copolymer (A-2) with method identical among the embodiment 1, different is that the control gas phase is formed so that ethylene/alpha-olefin copolymer (A-2) has MFR shown in the table 1 and density.
Embodiment 3
Polymerization
Obtain ethylene/alpha-olefin copolymer (A-3) with method identical among the embodiment 1, different is that the control gas phase is formed so that ethylene/alpha-olefin copolymer (A-3) has MFR shown in the table 1 and density.
Comparative example 1
Polymerization
Obtain ethylene/alpha-olefin copolymer (C-2) with preparation method identical among the embodiment 1, different is that the control gas phase is formed so that ethylene/alpha-olefin copolymer (C-2) has MFR shown in the table 1 and density.
Comparative example 2
The preparation catalyst component
With prepare " prepare catalyst component " among the embodiment 1 in identical method prepare the solid catalyst component, the toluene solution (Zr:28.0 mmole/liter) that different is closes zirconium with 10.0 liters of dichloride two (1,3-dimethyl cyclopentadienyl) replaces 20.0 liters of dichloride two (methyl cyclopentadienyl) to close the toluene solution of zirconium (Zr:14.0 mmole/liter).
The preparation pre-polymerized catalyst
Obtain pre-polymerized catalyst with preparation method identical among the embodiment 1, the solid catalyst component that obtains in different being to use above-mentioned " preparation catalyst component ".
Polymerization
Obtain ethylene/alpha-olefin copolymer (D) with preparation method identical among the embodiment 1, the pre-polymerized catalyst that obtains in different being to use above-mentioned " preparation pre-polymerized catalyst ", and the control gas phase is formed so that ethylene/alpha-olefin copolymer (D) has MFR shown in the table 1 and density.
Embodiment 4
The ethylene/alpha-olefin copolymer (B-1) of preparation embodiment 1 gained is carried out melt kneading with the ethylene/alpha-olefin copolymer (C-1) for preparing embodiment 2 gained with the weight ratio of 80/20 ((B-1)/(C-1)), and granulation, obtain ethylene copolymer composition (A '-1).
The melt property of ethylene copolymer composition (A '-1) and other character are as shown in table 1.
Embodiment 5-8, comparative example 3 and 4
With diameter is that to be 26 single screw extrusion machine make thickness with the pellet of each in ethylene/alpha-olefin copolymer shown in the table 3 and the ethylene copolymer composition is 30 microns blown film for 20mm , L/D, preparation condition is that port mould diameter is that 25mm , die lip width are that 0.7 millimeter, airflow rate (single seam vane) are 90 liters/minute, rate of extrusion is that 9 gram/minute, blow-up ratio are 1.8, rate of withdraw is 2.4 meters/minute, and processing temperature is 200 ℃.The performance of film sees Table 3.
Embodiment 9
Prepare ethylene/alpha-olefin copolymer (A-4) and (A-5) by embodiment 1 identical method, control gas phase that different is forms so that ethylene/alpha-olefin copolymer (A-4) and (A-5) all have density shown in the table 1 and a MFR.Carry out melt kneading and granulation with ethylene/alpha-hydrocarbon copolymer (A-4) with (A-5) with the weight ratio of 60/40 ((A-4)/(A-5)), obtain ethylene copolymer composition (L-1).Make blown film by the method for embodiment 5 to 8 by the pellet of ethylene copolymer composition (L-1).The results are shown in Table 2 and table 3.
Embodiment 10
Prepare ethylene/alpha-olefin copolymer (A-6) by embodiment 1 identical method, different is that the control gas phase is formed so that ethylene/alpha-olefin copolymer (A-6) has density shown in the table 1 and MFR.The ethylene/alpha-olefin copolymer (A-5) that ethylene/alpha-olefin copolymer (A-6) and embodiment 9 are made carries out melt kneading and granulation with the weight ratio of 60/40 ((A-6)/(A-5)), obtains ethylene copolymer composition (L-2).Make blown film by the method for embodiment 5 to 8 by the pellet of ethylene copolymer composition (L-2).The results are shown in Table 2 and table 3.
Embodiment 11
Prepare ethylene/alpha-olefin copolymer (A-7) and (A-8) by embodiment 1 identical method, control gas phase that different is forms so that ethylene/alpha-olefin copolymer (A-7) and (A-8) all have density shown in the table 1 and a MFR.Carry out melt kneading and granulation with ethylene/alpha-olefin copolymer (A-7) with (A-8) with the weight ratio of 60/40 ((A-7)/(A-8)), obtain ethylene copolymer composition (L-3).Make blown film by the method for embodiment 5 to 8 by the pellet of ethylene copolymer composition (L-3).The results are shown in Table 2 and table 3.
Table 1
| The type of comonomer | X (mole %) | MFR (restraining/10 minutes) | Density (gram per centimeter 3) | Be dissolved in the component mark (weight %) of decane | *1 | Fusing point Tm (℃) | ||
| Preparation embodiment 1 | B-1 | The 1-hexene | 2.20 | 0.20 | 0.925 | 0.17 | 0.99 | 117.30 |
| Preparation embodiment 2 | C-1 | The 1-hexene | 2.50 | 1.50 | 0.925 | 0.15 | 0.99 | 116.50 |
| Embodiment 1 | A-1 | The 1-hexene | 2.60 | 1.10 | 0.924 | 0.20 | 1.08 | 117.10 |
| Embodiment 2 | A-2 | The 1-hexene | 2.10 | 1.50 | 0.928 | 0.12 | 0.76 | 118.30 |
| Embodiment 3 | A-3 | The 1-hexene | 3.50 | 1.90 | 0.915 | 0.29 | 2.52 | 114.40 |
| Embodiment 4 | A′-1 | The 1-hexene | 2.50 | 1.20 | 0.925 | 0.15 | 0.99 | 117.20 |
| Comparative example 1 | C-2 | The 1-hexene | 2.60 | 1.10 | 0.925 | 0.19 | 0.99 | 116.60 |
| Comparative example 2 | D | The 1-hexene | 2.50 | 1.00 | 0.923 | 0.21 | 1.19 | 115.40 |
| Embodiment 9 | A-4 | The 1-hexene | 3.20 | 0.39 | 0.912 | 0.32 | 3.36 | 109.80 |
| Embodiment 9 | A-5 | The 1-hexene | 0.80 | 30 | 0.945 | 0.03 | 0.37 | 128.60 |
| Embodiment 10 | A-6 | The 1-hexene | 3.00 | 0.48 | 0.915 | 0.29 | 2.52 | 111.60 |
| Embodiment 11 | A-7 | The 1-hexene | 2.80 | 0.32 | 0.921 | 0.21 | 1.43 | 113.50 |
| Embodiment 11 | A-8 | The 1-hexene | 1.80 | 48 | 0.932 | 0.38 | 1.24 | 119.80 |
*When 1:MFR≤10 restrain/10 minutes, the value of 80 * exp (100 (d-0.88))+0.1,
When MFR＞10 restrain/10 minutes, 80 * (MFR-9)
0.26The value of * exp (100 (d-0.88))+0.1.
*The value of 2:400 * d-248
*3:9.0 * MFR
-0.65Value
*4:2.2 * MFR
-0.84Value
*5:(0.039Ln (C-2)+0.0096) * value of x+2.87,
C: the carbonatoms of comonomer (1-hexene: 6)
X: the content of comonomer (mole %)
*6:(0.039Ln (C-2)+0.1660) * value of x+2.87,
C: the carbonatoms of comonomer (1-hexene: 6)
X: the content of comonomer (mole %)
Table 1 (continuing)
| *2 | MT (gram) | *3 | *4 | Ea×10 -4 (J/molK) | *5 | *6 | M w/M n | ||
| Preparation embodiment 1 | B-1 | 122.00 | 21.40 | 25.60 | 8.50 | 3.08 | 3.01 | 3.35 | 2.60 |
| Preparation embodiment 2 | C-1 | 122.00 | 1.20 | 7.00 | 1.60 | 3.01 | 3.03 | 3.42 | 2.00 |
| Embodiment 1 | A-1 | 121.60 | 3.70 | 8.40 | 2.00 | 3.04 | 3.04 | 3.44 | 2.20 |
| Embodiment 2 | A-2 | 123.20 | 3.30 | 7.00 | 1.60 | 3.02 | 3.00 | 3.33 | 2.20 |
| Embodiment 3 | A-3 | 118.00 | 3.00 | 5.90 | 1.30 | 3.15 | 3.09 | 3.64 | 2.30 |
| Embodiment 4 | A′-1 | 122.00 | 3.40 | 8.00 | 1.90 | 3.05 | 3.03 | 3.42 | 2.33 |
| Comparative example 1 | C-2 | 122.00 | 1.60 | 8.40 | 2.00 | 3.05 | 3.04 | 3.44 | 2.00 |
| Comparative example 2 | D | 121.20 | 3.50 | 9.00 | 2.20 | 3.51 | 3.03 | 3.42 | 2.80 |
| Embodiment 9 | A-4 | 116.80 | 10.80 | 16.60 | 4.90 | 3.10 | 3.07 | 3.57 | 2.20 |
| Embodiment 9 | A-5 | 130.00 | - | - | - | - | - | - | 2.10 |
| Embodiment 10 | A-6 | 118.00 | 10.10 | 14.50 | 4.10 | 3.08 | 3.06 | 3.53 | 2.30 |
| Embodiment 11 | A-7 | 120.40 | 11.50 | 18.90 | 5.70 | 3.08 | 3.05 | 3.49 | 2.20 |
| Embodiment 11 | A-8 | 124.80 | - | - | - | - | - | - | 2.00 |
*When 1:MFR≤10 restrain/10 minutes, the value of 80 * exp (100 (d-0.88))+0.1,
When MFR＞10 restrain/10 minutes, 80 * (MFR-9)
0.26The value of * exp (100 (d-0.88))+0.1.
*The value of 2:400 * d-248
*3:9.0 * MFR
-0.65Value
*4:2.2 * MFR
-0.84Value
*5:(0.039Ln (C-2)+0.0096) * value of x+2.87,
C: the carbonatoms of comonomer (1-hexene: 6)
X: the content of comonomer (mole %)
*6:(0.039Ln (C-2)+0.1660) * value of x+2.87,
C: the carbonatoms of comonomer (1-hexene: 6)
X: the content of comonomer (mole %)
Table 2
| C-I | C-II | C-I/C-II | MFR (restraining/10 minutes) | Density (gram per centimeter 3) | MT (gram) | *3 | *4 | FI (1/ second) | *7 | ||
| Embodiment 9 | L-1 | A-4 | A-5 | 60/40 | 1.52 | 0.925 | 4.1 | 6.9 | 1.5 | 270 | 150 |
| Embodiment 10 | L-2 | A-6 | A-5 | 60/40 | 1.63 | 0.928 | 2.7 | 6.6 | 1.5 | 290 | 160 |
| Embodiment 11 | L-3 | A-7 | A-8 | 60/40 | 1.48 | 0.926 | 3.8 | 7.0 | 1.6 | 260 | 150 |
*3:9.0 * MFR
-0.65Value
*4:2.2 * MFR
-0.84Value
*The value of 7:100 * MFR
Table 3
| Mist degree (%) | *8 | FI (1/ second) | *7 | Glossiness (%) | Dart impact strength (N) | ||
| Embodiment 5 | A-1 | 3.90 | 4.7 | 90 | 110 | 93 | 3.77 |
| Embodiment 6 | A-2 | 4.20 | 4.7 | 120 | 150 | 92 | 3.21 |
| Embodiment 7 | A-3 | 3.40 | 3.8 | 150 | 190 | 98 | ＞10 |
| Embodiment 8 | A′-1 | 4.40 | 4.5 | 90 | 120 | 90 | 3.50 |
| Comparative example 3 | C-2 | 11.2 | 2.8 | 70 | 110 | 60 | 3.68 |
| Comparative example 4 | D | 8.9 | 4.5 | 350 | 100 | 56 | 2.30 |
| Embodiment 9 | L-1 | 7.7 | 9.9 | 270 | 152 | 74 | 3.89 |
| Embodiment 10 | L-2 | 6.5 | 8.4 | 290 | 163 | 85 | 3.33 |
| Embodiment 11 | L-3 | 7.0 | 9.7 | 260 | 148 | 79 | 3.91 |
*The value of 7:100 * MFR
*8:FI 〉=100MFR (FI: flow index, MFR: melt flow rate (MFR)):
The carbonatoms of alpha-olefin (C)=6:0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1Value
The carbonatoms of alpha-olefin (C)=7 or 8:0.50/ (1-d) * log (3 * MT
1.4) value
FI＜100MFR (FI: flow index, MFR: melt flow rate (MFR)):
The carbonatoms of alpha-olefin (C)=6:0.25/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1Value
The carbonatoms of alpha-olefin (C)=7 or 8:0.50/ (1-d) * log (3 * MT
1.4) value
(d: density (gram per centimeter
3), MT: melt tension (gram))
*9: formability
AA：MT≥3
BB：2≤MT＜3
CC：MT＜2
Table 3 (continuing)
| Formability *9 | MFR (restraining/10 minutes) | MT | Density (gram per centimeter 3) | Ea×10 -4 (J/molK) | ||
| Embodiment 5 | A-1 | AA | 1.10 | 3.70 | 0.924 | 3.04 |
| Embodiment 6 | A-2 | AA | 1.50 | 3.30 | 0.928 | 3.02 |
| Embodiment 7 | A-3 | AA | 1.90 | 3.30 | 0.915 | 3.15 |
| Embodiment 8 | A′-1 | AA | 1.20 | 3.40 | 0.925 | 3.05 |
| Comparative example 3 | C-2 | CC | 1.10 | 1.60 | 0.925 | 3.05 |
| Comparative example 4 | D | AA | 1.00 | 3.50 | 0.923 | 3.51 |
| Embodiment 9 | L-1 | AA | 1.52 | 4.10 | 0.925 | 3.11 |
| Embodiment 10 | L-2 | BB | 1.63 | 2.70 | 0.928 | 3.05 |
| Embodiment 11 | L-3 | AA | 1.48 | 3.80 | 0.926 | 3.09 |
*The value of 7:100 * MFR
*8:FI 〉=100MFR (FI: flow index, MFR: melt flow rate (MFR)):
The carbonatoms of alpha-olefin (C)=6:0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1Value
The carbonatoms of alpha-olefin (C)=7 or 8:0.50/ (1-d) * log (3 * MT
1.4) value
FI＜100MFR (FI: flow index, MFR: melt flow rate (MFR)):
The carbonatoms of alpha-olefin (C)=6:0.25/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1Value
The carbonatoms of alpha-olefin (C)=7 or 8:0.50/ (1-d) * log (3 * MT
1.4) value
(d: density (gram per centimeter
3), MT: melt tension (gram))
*9: formability
AA：MT≥3
BB：2≤MT＜3
CC：MT＜2
Claims (4)
1. an ethylene copolymer composition (A '), it comprises:
(B) ethylene/alpha-olefin copolymer and
(C) ethylene/alpha-olefin copolymer,
Described ethylene/alpha-olefin copolymer (B) is ethene and the multipolymer that contains the alpha-olefin of 6 to 8 carbon atoms, has following character:
(B-i) density is at the 0.880-0.970 gram per centimeter
3Scope in,
(B-ii) at the melt flow rate (MFR) MFR under 190 ℃, 2.16 kilograms the load in/10 minutes scope of 0.02-200 gram,
(B-iii) component mark W and the density d that is dissolved in decane under the room temperature satisfies following relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.26* exp (100 (d-0.88))+0.1
(B-iv) the temperature T m of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter and density d satisfy following relation:
Tm＜400×d-248，
(B-v) melt tension MT 190 ℃ time the and melt flow rate (MFR) MFR satisfy following relation:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
(B-vi) the flow-activation energy Ea that is determined by the synergetic shift factor of the time-temperature of flow curve, its unit be * 10
-4The content x of alpha-olefin in the carbonatoms C of alpha-olefin and the multipolymer in J/molK, the multipolymer, its unit are that the % mole satisfies following relation:
(0.039 Ln(C-2)+0.0096)×x+2.87＜(Ea)×10
-4≤(0.039 Ln(C-2)+0.1660)×x+2.87
And
(B-vii) the weight-average molecular weight M that records by GPC
wWith number-average molecular weight M
nRatio M
w/ M
nMeet the following conditions:
2.2＜M
w/M
n＜3.5；
Described ethylene/alpha-olefin copolymer (C) is ethene and the multipolymer that contains the alpha-olefin of 6 to 8 carbon atoms, has following character:
(C-i) density is at the 0.880-0.970 gram per centimeter
3Scope in,
(C-ii) at the melt flow rate (MFR) MFR under 190 ℃, 2.16 kilograms the load in/10 minutes scope of 0.02-200 gram,
(C-iii) component mark W and the density d that is dissolved in decane under the room temperature satisfies following relation:
Under MFR≤situation of/10 minutes of 10 grams, W＜80 * exp (100 (d-0.88))+0.1
Under MFR＞situation of/10 minutes of 10 grams, W＜80 * (MFR-9)
0.26* exp (100 (d-0.88))+0.1
(C-iv) the temperature T m of the multipolymer endothermic curve maximum peak position that records with differential scanning calorimeter and density d satisfy following relation:
Tm＜400×d-248，
And
(C-v) melt tension MT 190 ℃ time the and melt flow rate (MFR) MFR satisfy following relation:
MT≤2.2×MFR
-0.84；
Wherein, the ratio of the melt flow rate (MFR) MFR (B) of the melt flow rate (MFR) MFR (C) of multipolymer (C) and multipolymer (B) meets the following conditions:
1＜(MFR(C))/(MFR(B))≤20。
2. ethylene copolymer composition as claimed in claim 1 (A '), therein ethylene/alpha-olefin copolymer (B) and (C) all be ethene/1-hexene copolymer, described ethylene copolymer composition (A ') has following character:
(A '-i) melt tension MT and the melt flow rate (MFR) MFR 190 ℃ the time meets the following conditions:
9.0×MFR
-0.65＞MT＞2.2×MFR
-0.84，
(A '-the flow-activation energy Ea that ii) determines by the synergetic shift factor of the time-temperature of flow curve, its unit is * 10
-4J/molK, multipolymer (B) and (C) in the carbonatoms C of 1-hexene and multipolymer (B) and (C) in the total content x of 1-hexene, its unit is that the % mole satisfies following the relation:
(0.039 Ln(C-2)+0.0096)×x+2.87＜(Ea)×10
-4≤(0.039 Ln(C-2)+0.1660)×x+2.87
And
(A '-mist degree of the film of 30 micron thickness that iii) made with blow moulding by described copolymer compositions meets the following conditions:
Flow index FI and melt flow rate (MFR) MFR satisfy and concerns under the situation of FI 〉=100 * MFR, and described flow index FI is defined as and works as shear-stress reach 2.4 * 10 in the time of 190 ℃
6Dynes per centimeter
2The time given shearing rate,
Mist degree＜0.45/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
And
Flow index FI and melt flow rate (MFR) MFR satisfy and concerns under the situation of FI＜100 * MFR, and described flow index FI is defined as and works as shear-stress reach 2.4 * 10 in the time of 190 ℃
6Dynes per centimeter
2The time given shearing rate,
Mist degree＜0.25/ (1-d) * log (3 * MT
1.4) * (C-3)
0.1
Wherein, d represents density, and unit is a gram per centimeter
3, MT represents melt tension, and unit is a gram, and C represents the carbonatoms of 1-hexene, promptly 6.
3. ethylene copolymer composition as claimed in claim 2 (A '), it also has following character:
(A '-the weight-average molecular weight M that iv) records by GPC
wWith number-average molecular weight M
nRatio M
w/ M
nMeet the following conditions:
2.0≤M
w/M
n≤2.5。
4. ethylene copolymer composition comprises:
(A ') as each described ethylene copolymer composition in the claim 1 to 3, and
(D) ethylene/alpha-olefin copolymer, it is to be made by ethene and the alpha-olefin copolymer that contains 3 to 20 carbon atoms in the presence of olefin polymerization catalysis, described catalyzer comprises (a) Organoaluminoxy compound and (b-III) contains the transistion metal compound of periodictable the 4th group 4 transition metal of the ligand with cyclopentadienyi skeleton, and described ethylene/alpha-olefin copolymer has following character:
(D-i) density is at the 0.850-0.980 gram per centimeter
3Scope in, and
(D-ii) limiting viscosity that records in naphthane 135 ℃ the time is in the scope of 0.4-8dl/g;
Condition is ethylene/alpha-olefin copolymer (B) and (C) all is different from ethylene/alpha-olefin copolymer (D).
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP358272/1997 | 1997-12-25 | ||
| JP358272/97 | 1997-12-25 | ||
| JP35827297 | 1997-12-25 | ||
| JP48121/1998 | 1998-02-27 | ||
| JP48121/98 | 1998-02-27 | ||
| JP4812198 | 1998-02-27 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98126228A Division CN1114627C (en) | 1997-12-25 | 1998-12-25 | Ethylene/α-olefin copolymer and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1491981A CN1491981A (en) | 2004-04-28 |
| CN1226341C true CN1226341C (en) | 2005-11-09 |
Family
ID=29551504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021228094A Expired - Lifetime CN1226341C (en) | 1997-12-25 | 1998-12-25 | Ethylene copolymer composition |
Country Status (6)
| Country | Link |
|---|---|
| KR (1) | KR100327177B1 (en) |
| CN (1) | CN1226341C (en) |
| CA (1) | CA2256796A1 (en) |
| DE (1) | DE69829106T2 (en) |
| ID (1) | ID21611A (en) |
| TW (1) | TW542844B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2103380C (en) * | 1992-11-19 | 2002-07-02 | Mitsui Chemicals, Inc. | Ethylene/.alpha.-olefin copolymer composition, graft modified ethylene/.alpha.-olefin copolymer composition, ethylene copolymer composition, and multi-stage olefin polymerization process |
-
1998
- 1998-12-21 TW TW087121330A patent/TW542844B/en not_active IP Right Cessation
- 1998-12-22 CA CA002256796A patent/CA2256796A1/en not_active Abandoned
- 1998-12-23 DE DE69829106T patent/DE69829106T2/en not_active Expired - Lifetime
- 1998-12-23 ID IDP981666A patent/ID21611A/en unknown
- 1998-12-24 KR KR1019980058163A patent/KR100327177B1/en not_active Expired - Lifetime
- 1998-12-25 CN CNB021228094A patent/CN1226341C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| TW542844B (en) | 2003-07-21 |
| DE69829106T2 (en) | 2006-02-09 |
| KR19990063415A (en) | 1999-07-26 |
| CA2256796A1 (en) | 1999-06-25 |
| KR100327177B1 (en) | 2002-12-06 |
| CN1491981A (en) | 2004-04-28 |
| ID21611A (en) | 1999-07-01 |
| DE69829106D1 (en) | 2005-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1226563A (en) | Ethylene/alpha-olefin copolymer and process for producing the same | |
| CN1063763C (en) | Olefin polymer composition | |
| CN1109716C (en) | Polypropylene resin composition and non-stretched film thereof | |
| CN1122075C (en) | Resin composition and its application | |
| CN1042433C (en) | Process for the preparation of olefin polymers | |
| CN1076282C (en) | Polypropylene composite film | |
| CN1239659C (en) | Bonded copolyvinyls resin compsn and laminate contg same | |
| CN1122074C (en) | Ethylenic polymer composition | |
| CN100344657C (en) | Ethylenic polymer and application thereof to molded product | |
| CN1220672A (en) | Olefin polymerization catalyst and process for production of olefin polymers | |
| CN1100429A (en) | Olefin polymerization catalysts and methods of olefin polymerization | |
| CN1233558A (en) | Laminated film | |
| CN1120856C (en) | Resin composition and use thereof | |
| CN1388809A (en) | Butene copolymer, resin composition thereof, moldings made therefrom, solid titanium catalyst and method for its preparation | |
| CN1121079A (en) | Olefin polymerization catalyst and process for olefin polymerization | |
| CN1098887C (en) | Shrinkable film made from olefine copolymer | |
| CN1287561A (en) | Ethylene / aromatic vinyl copolymer and process for producing the same | |
| CN1208050A (en) | Olefin thermoplastic elastomer composition | |
| CN1118511C (en) | Flexible resin composition and its use | |
| CN1075020C (en) | Internal container of case and method for packing and transporting liquid material | |
| CN1028763C (en) | Ethylene/ pentene-1 copolymer composition | |
| CN1059451C (en) | Polypropylene film | |
| CN1226341C (en) | Ethylene copolymer composition | |
| CN1295595A (en) | Water barrier sheet | |
| CN1280999A (en) | Contraction film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20051109 |
|
| CX01 | Expiry of patent term |