CN1395583A - 三元共聚物 - Google Patents
三元共聚物 Download PDFInfo
- Publication number
- CN1395583A CN1395583A CN01803836A CN01803836A CN1395583A CN 1395583 A CN1395583 A CN 1395583A CN 01803836 A CN01803836 A CN 01803836A CN 01803836 A CN01803836 A CN 01803836A CN 1395583 A CN1395583 A CN 1395583A
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- CN
- China
- Prior art keywords
- product
- diolefine
- ethene
- mfr
- carbon atom
- 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.)
- Pending
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- 229920001897 terpolymer Polymers 0.000 title claims description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical group C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000001993 dienes Chemical group 0.000 claims description 4
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 claims 4
- 229920005684 linear copolymer Polymers 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 229920000092 linear low density polyethylene Polymers 0.000 abstract description 3
- 239000004707 linear low-density polyethylene Substances 0.000 abstract description 3
- 230000004075 alteration Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 239000007787 solid Substances 0.000 description 14
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- 235000012239 silicon dioxide Nutrition 0.000 description 10
- 229960001866 silicon dioxide Drugs 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- -1 tetrahydro indenyl Chemical group 0.000 description 5
- HITROERJXNWVOI-SOFGYWHQSA-N (5e)-octa-1,5-diene Chemical compound CC\C=C\CCC=C HITROERJXNWVOI-SOFGYWHQSA-N 0.000 description 4
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000005243 fluidization Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- LZRCZQUJFIJGIO-UHFFFAOYSA-N C[Hf](C)C1C=CC=C1 Chemical compound C[Hf](C)C1C=CC=C1 LZRCZQUJFIJGIO-UHFFFAOYSA-N 0.000 description 1
- SNQFNJBZYZBXGD-UHFFFAOYSA-L Cl[Hf](Cl)C1C=CC=C1 Chemical compound Cl[Hf](Cl)C1C=CC=C1 SNQFNJBZYZBXGD-UHFFFAOYSA-L 0.000 description 1
- XJONFIGVOQMBIP-UHFFFAOYSA-L Cl[Zr](Cl)C1C=CC=C1 Chemical class Cl[Zr](Cl)C1C=CC=C1 XJONFIGVOQMBIP-UHFFFAOYSA-L 0.000 description 1
- ZBKJVVTWGPHNSC-UHFFFAOYSA-L Cl[Zr]Cl.C[C]1C(C)=C(C)C(C)=C1C Chemical compound Cl[Zr]Cl.C[C]1C(C)=C(C)C(C)=C1C ZBKJVVTWGPHNSC-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- PDYRUWWTQSUFOR-UHFFFAOYSA-L [Cl-].[Cl-].C(C(C)C)C1(C=CC=C1)[Zr+2] Chemical compound [Cl-].[Cl-].C(C(C)C)C1(C=CC=C1)[Zr+2] PDYRUWWTQSUFOR-UHFFFAOYSA-L 0.000 description 1
- NKKALSOFYFMKGW-UHFFFAOYSA-L [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] Chemical compound [Cl-].[Cl-].C(CCC)C1=CC=CC1[Zr+2] NKKALSOFYFMKGW-UHFFFAOYSA-L 0.000 description 1
- UCIKZESDXASJNG-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 Chemical compound [Cl-].[Cl-].C1=CC=C2C([Zr+2])C=CC2=C1 UCIKZESDXASJNG-UHFFFAOYSA-L 0.000 description 1
- XUPZHUANNZZNDR-UHFFFAOYSA-L [Cl-].[Cl-].CC1=C(C(=C(C1(C)[Hf+2])C)C)C Chemical compound [Cl-].[Cl-].CC1=C(C(=C(C1(C)[Hf+2])C)C)C XUPZHUANNZZNDR-UHFFFAOYSA-L 0.000 description 1
- QMUDOHCFQLGPLF-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC=CC1(C)[Zr++] Chemical compound [Cl-].[Cl-].CC1=CC=CC1(C)[Zr++] QMUDOHCFQLGPLF-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012725 vapour phase polymerization Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004711 α-olefin 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
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT 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
- C08F4/6592—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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
本发明涉及向聚合物中引入长链支化的线性低密度聚乙烯的改性，该线性低密度聚乙烯通常没有长链支化。
Description
发明领域
本发明涉及如下物质的三元共聚物：乙烯，3-10个碳原子、优选4-10个碳原子的0烯烃，和包含7-10个碳原子的二烯烃。二烯烃的存在符合在三元共聚物中的长链支化；没有二烯烃的共聚物不显示长链支化。当它增加获得聚合产物的加工性能时，长链支化是所需的。
发明概述
已经使用负载活化金属茂催化剂生产乙烯，α烯烃，和二烯烃的三元共聚物。金属茂催化剂的使用导致取代烯烃的高共聚单体引入。非常少量的二烯烃引起树脂MFR[I21/I2，根据ASTM D-1238，条件E和F测量]的显著变化而没有Mw/Mn的显著变化(与没有任何二烯烃的对应树脂相比)。树脂MFR的此变化和基本恒定的Mw/Mn是树脂中引入长链支化的指示。
发明详述
本发明涉及三元共聚物，它包含乙烯单元，α烯烃单元和作为第三组分的包含7-10个、优选7-9个碳原子的二烯烃。这些三元共聚物包含至少80wt％，通常至少90wt％乙烯单元。该三元共聚物包含至多20wt％的3-10个碳原子的α烯烃和0.1-20wt％的7-10个碳原子的二烯烃。产物的α构造
除乙烯之外，使用的单体包括C3-C10α-烯烃。优选，产物包含至少8αwt％乙烯单元。在本发明中与乙烯一起使用的α烯烃，α-单烯烃优选包含3-8个碳原子。合适的α烯烃包括丙烯、丁烯-1、戊烯-1、己烯-1、4-甲基戊烯-1、庚烯-1、辛烯-1及其混合物。优选，α烯烃共聚单体包括1-丁烯、1-己烯、1-辛烯及其混合物。最优选的α烯烃是己烯-1。乙烯和α烯烃结合的特定例子是乙烯/1-丁烯、乙烯/1-己烯、乙烯/4-甲基-1-戊烯、乙烯/1-丁烯/1-己烯、乙烯/丙烯/1-己烯和乙烯/丙烯/1-丁烯。在本发明的聚合反应中可以使用氢气作为链转移剂。对于催化剂和反应物为惰性的任何气体也可以存在于气体流中。
二烯烃优选包含6-10个碳原子，优选7-9个碳原子。二烯烃的例子包括1，6-庚二烯、1，7-辛二烯、1，8-壬二烯，与7-9个碳原子的二烯烃对MFR的变化相比，1，5-己二烯和9-癸二烯也用于本发明，但具有更少的效果。
在如下所述催化剂存在下，优选在淤浆下或更优选在下述流化床气相催化聚合条件下，制备这些产物。
产物包含0.1-2ppm过渡金属，如锆。产物也包含5-100ppm，优选10-50ppm铝。产物的过渡金属，如锆和铝含量可归因于催化剂残余物。用于制备本发明产物的催化剂是由铝氧烷活化的锆的金属茂。
产物的特征在于如下的密度：小到0.88和至多小于0.965和优选小于0.94g/cm3。对于在此的用途，密度大于约0.88，一般大于0.900至多小于0.965，优选约0.90-0.93g/cm3。
本发明的产物显示如下的MI：它可至多为150和至多300，如0.01-300。
本发明的低密度产物显示如下的熔体流动比(MFR)：至少16，优选16-60，和最优选16-45。MFR是比例I21/I2[其中I21根据ASTM D-1238，条件F在190℃下测量和I2根据ASTM D-1238，条件E在190℃下测量]。
这些产物的Mw/Mn为约2.0-约3.5。Mw是重均分子量和Mn是数均分子量，它们每一个从分子量分布通过GPC(凝胶渗透色谱)计算。已经生产如下的Mw/Mn产物：小于2.5，在2.0-3.5范围，优选2-3。催化剂
用于生产本发明树脂的催化剂组合物包含一种以金属茂提供的过渡金属。催化剂包括载体、助催化剂的活化剂和至少一种金属茂。
载体材料是固体、微粒、多孔、无机或有机材料，但优选无机材料，如硅和/或铝的氧化物。载体材料以平均粒度为约1微米-约250微米，优选约10微米-约150微米的干燥粉末使用。如需要，可对处理的载体材料进行筛分以保证粒子的平均粒度优选小于150微米。在形成窄分子量分布的LLDPE中这是非常需要的，以降低凝胶。载体的表面积至少为约3平方米/克(m2/g)，和优选至少约50m2/g至多约350m2/g。当载体是二氧化硅时，将它优选加热到约100℃-约850℃和最优选约250℃。载体材料必须含有至少一些活性羟基(OH)以生产本发明的催化剂组合物。
在最优选的实施方案中，载体是二氧化硅，在它的使用之前在第一催化剂合成步骤中，已经通过将它采用氮气流态化和在约250℃下加热约4小时而脱水，以达到约1.8毫摩尔/克(mmol/g)的表面羟基浓度。最优选实施方案的二氧化硅是高表面积、非晶二氧化硅(表面积＝300m2/g；孔体积为1.65cm3/g)，和它是由Davison Chemical Divisionof W.R.Grace and Company以商品名Davison 952-1836、Davison 952或Davison 955市售的材料。
为形成催化剂，可以将所有的催化剂前体组分与活化剂或助催化剂如铝氧烷溶解和与载体反应。在如下所述的工艺中，将载体材料与铝氧烷溶液，优选甲基铝氧烷反应。铝氧烷类别包括由如下通式表示的低聚线性和/或环状烷基铝氧烷：
低聚、线性铝氧烷的R-(Al(R)-O)n-AlR2和
低聚、环状铝氧烷的(-Al(R)-O)m
其中n是1-40，优选10-20，m是3-40，优选3-20和R是C1-C8烷基和优选甲基。甲基铝氧烷(MAO)是分子量分布非常宽和平均分子量通常为约1000的低聚物的混合物。MAO典型地保持在甲苯的溶液中。
在铝氧烷的一个实施方案中，向载体的引入依赖于二氧化硅的孔体积。在此实施方案中，浸渍载体材料的工艺是通过铝氧烷溶液的浸渍，而不在铝氧烷溶液中形成载体材料，如二氧化硅的淤浆。铝氧烷溶液的体积足够填充载体材料的孔体积，而不形成淤浆，其中溶液体积超过二氧化硅的孔体积；因此和优选，铝氧烷溶液的最大体积是和不超过载体材料样品的总孔体积。[已经发现在浸渍期间，可以使用基于二氧化硅孔至多30％过量的溶剂体积而不产生二氧化硅淤浆。]铝氧烷溶液的该最大体积保证不形成二氧化硅的淤浆。因此，如果载体材料的孔体积是1.65cm3/g，则铝氧烷的体积等于或小于载体材料的1.65cm3/g。由于此条件，尽管载体的孔尤其被溶剂填充，在浸渍之后浸渍的载体材料立即干燥。
通过加热和/或在由惰性气体、如氮气引起的正压下，可以从载体材料的铝氧烷浸渍孔除去溶剂。如采用，控制在此步骤中的条件以降低，如果不消除，浸渍载体粒子的附聚和/或铝氧烷的交联。在此步骤中，可以通过蒸发除去溶剂，蒸发在约40℃以上和约50℃以下的相对低的升高温度下进行。尽管可以在比由约40℃-约50℃定义的相对更高温度下，通过蒸发除去溶剂，但必须采用非常短的加热时间进度。
在优选的实施方案中，在将载体与溶液反应之前，将金属茂加入到铝氧烷的溶液中。也包括金属茂的铝氧烷溶液的最大体积可以是载体材料样品的总孔体积。铝氧烷提供的铝，表示为Al，对表示为M(如Zr)的金属茂金属的摩尔比为50-500，优选75-300，和最优选100-200。本发明的另外优点在于可以直接控制Al∶Zr比例。在进一步优选的实施方案中，在与载体的反应之前，在约20℃-80℃的温度下，将铝氧烷和金属茂化合物混合在一起0.1-6.0小时。用于金属茂和铝氧烷的溶剂可以是合适的溶剂，如芳族烃、卤代烃或卤代芳族烃，优选甲苯。
在催化剂的另外合成中，可以将铝氧烷溶液体积接触的载体在第二溶剂中分散。另外浸渍工艺的关键方面是除铝氧烷溶液以外，第二液体介质的使用。液体介质是包含5-20个碳原子的烃。可用作液体介质的说明性化合物包括戊烷、异戊烷、己烷、异己烷、庚烷、辛烷、壬烷、癸烷、十二烷、环戊烷、环己烷、和环庚烷或其混合物。也可以使用这些烃的异构体。在另外合成中第二液体介质的体积也是关键的在于此体积必须足以形成淤浆。一般情况下，此体积应当为由氮气吸附法(BET方法)测量的载体孔体积的2-15倍。例如，对于1.5cc/g孔体积的二氧化硅载体，采用最小3cc第二介质，如己烷和最大20cc/g二氧化硅。
金属茂化合物具有通式CpmMAnBp，其中Cp是未取代或取代环戊二烯基，M是锆或铪和A和B属于卤原子、氢或烷基。在金属茂化合物的以上通式中，优选的过渡金属原子M是锆，在金属茂化合物的以上通式中，Cp是未取代、单或多取代环戊二烯基。在环戊二烯基上的取代基可以优选是直链或支化C1-C6烷基。环戊二烯基也可以是双环或三环结构如茚基、四氢茚基、芴基或部分氢化芴基的一部分，以及取代双环或三环结构的一部分。在金属茂化合物以上通式中m等于2的情况下，环戊二烯基也可以由如下多亚甲基或二烷基硅烷基团桥接：如-CH2-、-CH2-CH2-、-CR’R”-和-CR’R”-CR’R”-，其中R’和R”是短烷基或氢、-Si(CH3)2-、-Si(CH3)2-CH2-CH2-Si(CH3)2-和相似的桥接基团。如果在金属茂化合物以上通式中的A和B取代基是卤原子，它们属于氟、氯、溴或碘。如果在金属茂化合物以上通式中的A和B取代基是烷基或芳族基团，它们优选是直链或支化C1-C8烷基，如甲基、乙基、正丙基、异丙基、正丁基、异丁基、正戊基、正己基或正辛基。
合适的金属茂化合物包括双(环戊二烯基)金属二卤化物、双(环戊二烯基)金属氢卤化物(hydridohalide)、双(环戊二烯基)金属单烷基单卤化物、双(环戊二烯基)金属二烷基和双(茚基)金属二卤化物，其中金属是钛、锆或铪，卤化物基团优选是氯和烷基是C1-C6烷基。金属茂的说明性，但非限制性例子是双(环戊二烯基)二氯化锆、双(环戊二烯基)二氯化铪、双(环戊二烯基)二甲基锆、双(环戊二烯基)二甲基铪、双(环戊二烯基)氢氯化锆、双(环戊二烯基)氢氯化铪、双(五甲基环戊二烯基)二氯化锆、双(五甲基环戊二烯基)二氯化铪、双(正丁基环戊二烯基)二氯化锆、双(异丁基环戊二烯基)二氯化锆、双(二甲基环戊二烯基)二氯化锆、环戊二烯基三氯化锆、双(茚基)二氯化锆、双(4，5，6，7-四氢-1-茚基)二氯化锆、和亚乙基-[双(4，5，6，7-四氢-1-茚基)]二氯化锆。在此技术的实施方案中采用的金属茂化合物可以结晶固体、以在芳族烃中的溶液或以负载的形式使用。
将以微粒形式包括金属茂化合物和铝氧烷的催化剂加入到用于气相聚合以及乙烯和高级α烯烃共聚的流化床反应器中。工艺条件
当在气相、流化床中进行聚合时，必要的是在低于聚合物粒子烧结温度的温度下操作流化床反应器。为保证不发生烧结，低于烧结温度的温度是所需的。对于在本发明方法中乙烯聚合物的生产，优选是对于烯烃聚合的约60℃-115℃的操作温度，和最优选是约75℃-95℃的温度。
反应器在约100-350psi的压力下操作。
在流化床反应器中，气相反应混合物通过床的表观气体速度必须超过流化要求的最小流速，和优选在最小流速以上至少0.2英寸/秒。与共聚单体一起采用稀释剂”气体，在聚合反应器中的条件下它是非反应性的。稀释剂气体可以是氮气、氩气、氦气、甲烷、乙烷等。通常表观气体速度不超过5.0英尺/秒，和最通常不大于2.5英尺/秒是足够的。将气态单体的原料物流，有或没有惰性气体稀释剂，在约2-10磅/小时/立方英尺的床体积的空时收率下，加入到反应器中。
在上述优选催化剂存在下，在气相流化床工艺中，生产共聚物产物。
对于膜生产，产物可包含通常加入到聚合物组合物中的任何各种添加剂，如润滑剂、微滑石、稳定剂、抗氧剂、相容剂、颜料等。可以采用这些试剂以稳定产物抗氧化。可以将本发明产物与如下密度为0.910-0.97g/cc的另一种乙烯线性聚合物或共聚物共混：例如，其它线性聚合物或共聚物可以是由自由基聚合，在超过350ps i压力下生产的物质。可以将聚合物直接加入到吹膜挤出机，如Sterling挤出机中，以生产厚度，例如为约0.5-5密耳的膜。
如下实施例进一步说明本发明的必须特征。然而，对于本领域技术人员显然的是用于实施例的具体试剂和反应条件并不限制本发明的范围。
在实施例中生产的聚合物性能通过如下测试方法测量：密度 ASTM D-1505-制备试片和在100℃下调节1小
时以达到平衡结晶度。然后在密度梯度柱中
测量密度；报导为gms/cc。熔融指数(MI)，I2 ASTM D-1238-条件E
在190℃下测量-报导为克/10分钟高负荷HLMI，I21 ASTM D-1238-条件F
在用于以上熔融指数测试的10.5倍重量下测
量熔体流动比(MFR)＝ I21/I2
所有的步骤在干燥氮气气氛下进行。所有液体/溶剂是无水的。在JEOL Eclipse 400上，在100.4MHz下，在定量条件下，记录13C NMR光谱。负载在二氧化硅上的(BuCp)2ZrCl2和甲基铝氧烷(MAO)催化剂用于聚合。
乙烯/1-己烯/二烯烃三元共聚物通过下述聚合步骤制备。1-己烯和二烯烃浓度如描述变化。相同地制备乙烯/二烯烃共聚物，但没有1-己烯。
在室温下，向1加仑不锈钢高压釜中加入1500mL庚烷，150mL的1-己烯，10mL的1，7-辛二烯，和1.0mL的在己烷中的14wt％三异丁基铝。关闭反应器，和将温度变成70℃。采用乙烯压力将26.6mg催化剂引入。按需要再装入乙烯以保持反应器压力恒定为130psi。在60分钟之后，将反应器排空和冷却到室温。收集37克聚合物。将聚合物在真空烘箱中干燥以除去残余的挥发性烃，在辊炼机上于160℃下熔融均化，和采用抗氧剂稳定。
使用在催化剂中描述的负载金属茂/MAO催化剂，生产乙烯、己烯、和长链二烯烃的三元共聚物。非常少量的二烯烃，特别是1，7-辛二烯，引起树脂MFR的显著变化而Mw/Mn没有显著变化。MFR的此增加是长链支化存在的指示，如在U.S.专利5,272,236中描述的那样，该文献在此引入作为参考。
在相同的淤浆条件下，将1，5-己二烯，1，7-辛二烯，1，9-癸二烯，和1-癸烯与己烯和乙烯三元共聚，和将这样的三元共聚物在表1中提及。
表1
| 三元共聚单体 | 无 | 1，5-C6 | 1，7-C8 | 1，9-C10 | C10 |
| g/g/hr/100psi产率 | 1900 | 1800 | 1200 | 2300 | 2400 |
| MI | 0.36 | 0.59 | 0.37 | 1.0 | 0.46 |
| MFR | 16.9 | 21.2 | 34.1 | 25.9 | 18.7 |
| 密度(g/mL) | 0.908 | 0.910 | 0.913 | 0.909 | 0.909 |
| Mw/Mn | 2.55 | 2.44 | 3.01 | 3.44 | 2.51 |
| 摩尔％C6 | 3.1 | 3.3 | 3.3 | 3.8 | 3.1 |
| Tm(C) | 100 | 100，110 | 102，118 | 10.1 | 100，113 |
(5.0mL三元共聚单体用于每种情况。1.5-C6是1，5-己二烯，1.7-C8是1，7-辛二烯，1.9-C10是1，9-癸二烯，C10是癸烯)
少量1，7-辛二烯或1，9-癸二烯得到MFR为从17到25-35的树脂，不显著影响MI、密度、％C6、熔点、或Mw/Mn。乙烯、己烯和低水平癸烯的三元共聚产生没有显著不同于乙烯和己烯共聚物的聚合物。1，5-己二烯三元共聚物与乙烯/1-己烯共聚物对照变化较小。
生产乙烯和二烯烃的共聚物，如表2所示。1，7-辛二烯共聚物显示在任何这些二烯烃聚合物中最高的MFR。
表2
| 三元共聚单体 | 1，5-C6 | 1，7-C8 | 1，9-C10 | C10 |
| 共聚物产率g/g/hr/100psi | 560 | 710 | 800 | 850 |
| MI | 0.11 | 0.24 | 0.61 | 0.93 |
| MFR | 23.4 | 43.2 | 26.1 | 19.3 |
| Mw/Mn | 2.37 | 2.72 | 2.59 | 2.41 |
通过13C NMR分析共聚物。癸烯/乙烯产物确定为简单LLDPE共聚物，没有不寻常结构特征。NMR确认己二烯在1，5-己二烯/乙烯共聚物中成环以产生相似于环戊烯/乙烯共聚物的产物，如下所示：
1，7-辛二烯和1，9-癸二烯产物的NMR显示，在每个这些共聚物中存在多于一个的支化物质。然而，初步分析指示，在1，7-辛二烯共聚物中的支化水平至少为在1，9-癸二烯共聚物中该值的10倍。此观察结果与MFR数据相一致。
辛二烯浓度在聚合试验中变化，如表3所示。MFR在最高二烯烃水平下增加。
表3
| 辛二烯量(mL) | 0.5 | 5.0 | 10.0 | 20.0 |
| 产率g/＝g/hr/100psi | 2000 | 1200 | 1100 | 1200 |
| C6(mL) | 125 | 150 | 150 | 150 |
| I2 | 1.21 | 0.67 | 0.98 | 0.59 |
| MFR | 21.9 | 33.9 | 29.5 | 37.7 |
| Mw/Mn | 2.19 | 2.70 | 2.67 | 2.45 |
| 密度(g/mL) | 0.918 | 0.918 | 0.920 | 0.920 |
| ％C6 | 2.4 | 2.6 | 2.65 | 2.56 |
| Tm(C) | 107，121 | 106，120 | 106，123 | 108，121 |
Claims (9)
1.在包括乙烯和一定数量α烯烃的线性共聚物中，该共聚物没有长链支化，和显示16-20的MFR(I21/I2，根据ASTM D-1238测量)数值和2.0-3.5的Mw/Mn值，改性包括三元共聚物，该三元共聚物包含所述数量的α烯烃、所述乙烯和含7-10个碳原子的二烯烃单元，其中该二烯烃以有效增加MFR数值的量存在。
2.权利要求1的产物，其中三元共聚物显示基本相同于聚合物产物Mw/Mn的Mw/Mn。
3.权利要求1的产物，其中二烯烃选自1，7-辛二烯、1，8-壬二烯及其混合物。
4.一种将长链支化引入到聚合物组合物中的方法，该聚合物组合物没有长链支化和包括乙烯和3-10个碳原子的α单烯烃，和显示16-20的MFR(I21/I2，根据ASTM D-1238测量)数值和2.0-3.5的Mw/Mn值，该方法包括：
在催化剂存在下和在7-10个碳原子二烯烃存在下，在烯烃聚合条件下，将乙烯和α烯烃接触，
其中催化剂包括负载活化的过渡金属，其中过渡金属的来源以金属茂提供；
保持该Mw/Mn值同时增加MFR的数值；和
回收产物。
5.权利要求4的方法，其中二烯烃包含7-9个碳原子。
6.权利要求5的方法，其中产物显示小于0.94g/cc的密度。
7.权利要求6的方法，其中二烯烃选自1，7-辛二烯、1，8-壬二烯及其混合物。
8.由权利要求5的方法生产的产物。
9.由权利要求7的方法生产的产物。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/484,150 | 2000-01-18 | ||
| US09/484,150 US6509431B1 (en) | 2000-01-18 | 2000-01-18 | Terpolymers |
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| US (1) | US6509431B1 (zh) |
| EP (1) | EP1261651A1 (zh) |
| JP (1) | JP2003520870A (zh) |
| KR (1) | KR20020091084A (zh) |
| CN (1) | CN1395583A (zh) |
| BR (1) | BR0107651A (zh) |
| CA (1) | CA2397639A1 (zh) |
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| US20090163666A1 (en) * | 2007-12-21 | 2009-06-25 | David John Lohse | Polymer compositions exhibiting enhanced flow-induced crystallization |
| US9458310B2 (en) | 2009-10-16 | 2016-10-04 | Exxonmobil Chemical Patents Inc. | Modified polyethylene film compositions |
| US9321911B2 (en) | 2011-09-23 | 2016-04-26 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions for cast film |
| JP5960831B2 (ja) | 2011-09-23 | 2016-08-02 | エクソンモービル ケミカル パテンツ インコーポレイテッド | 改質ポリエチレン組成物 |
| US20160272798A1 (en) | 2011-09-23 | 2016-09-22 | Exxonmobil Chemical Patents Inc. | Modified Polyethylene Compositions with Enhanced Melt Strength |
| US9340664B2 (en) | 2011-09-23 | 2016-05-17 | Exxonmobil Chemical Patents Inc. | Modified polyethylene compositions for blown film |
| US8629217B2 (en) | 2011-11-22 | 2014-01-14 | Exxonmobil Chemical Patents Inc. | Modified polyethylene blown film compositions having excellent bubble stability |
| US10822479B2 (en) | 2012-09-20 | 2020-11-03 | Exxonmobil Chemical Patents Inc. | Foamed polyethylene compositions |
| US10836853B2 (en) | 2012-09-20 | 2020-11-17 | Exxonmobil Chemical Patents Inc. | Crack-resistant polyethylene compositions |
| CN104812828B (zh) | 2012-12-05 | 2016-10-12 | 埃克森美孚化学专利公司 | 具有优异的膜泡稳定性的hdpe 改性聚乙烯吹塑膜组合物 |
| JP2015532361A (ja) | 2013-06-28 | 2015-11-09 | エルジー・ケム・リミテッド | ジエンを含む三元系弾性共重合体およびその製造方法 |
| KR101585204B1 (ko) | 2013-06-28 | 2016-01-13 | 주식회사 엘지화학 | 디엔을 포함하는 3원계 탄성 공중합체 및 이의 제조 방법 |
| EP2883889A4 (en) | 2013-06-28 | 2016-06-01 | Lg Chemical Ltd | TERNARY ELASTIC COPOLYMER WITH A DIEN AND METHOD FOR THE PRODUCTION THEREOF |
| US9493593B2 (en) | 2013-06-28 | 2016-11-15 | Lg Chem, Ltd. | Elastic diene terpolymer and preparation method thereof |
| WO2015116382A1 (en) * | 2014-01-30 | 2015-08-06 | Exxonmobil Chemical Patents Inc. | Foamed polyethylene compositions |
| CN106414568B (zh) | 2014-05-29 | 2019-08-06 | 埃克森美孚化学专利公司 | 聚乙烯薄膜及其生产 |
| US10124528B2 (en) | 2014-05-29 | 2018-11-13 | Exxonmobil Chemical Patents Inc. | Cyclic-diene additives in polyethylene films and enhanced film orientation balance in production thereof |
| US10125247B2 (en) | 2014-05-29 | 2018-11-13 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions |
| CN110582536A (zh) | 2017-03-29 | 2019-12-17 | 埃克森美孚化学专利公司 | 聚乙烯组合物 |
| US10550252B2 (en) | 2017-04-20 | 2020-02-04 | Chevron Phillips Chemical Company Lp | Bimodal PE resins with improved melt strength |
| KR20210068075A (ko) * | 2018-09-28 | 2021-06-08 | 다우 글로벌 테크놀로지스 엘엘씨 | 4작용성 장쇄 분지형 에틸렌계 중합체 |
| JP2022501473A (ja) * | 2018-09-28 | 2022-01-06 | ダウ グローバル テクノロジーズ エルエルシー | 四官能性長鎖分岐状エチレン系ポリマー |
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| CA980498A (en) * | 1971-04-16 | 1975-12-23 | Du Pont Of Canada Limited | Ethylene polymers with long chain branching |
| EP0287666B1 (en) | 1986-09-24 | 1993-05-26 | Mitsui Petrochemical Industries, Ltd. | Process for polymerizing olefins |
| US5272236A (en) * | 1991-10-15 | 1993-12-21 | The Dow Chemical Company | Elastic substantially linear olefin polymers |
| US5241031A (en) | 1992-02-19 | 1993-08-31 | Exxon Chemical Patents Inc. | Elastic articles having improved unload power and a process for their production |
| US5502127A (en) | 1994-03-31 | 1996-03-26 | Union Carbide Chemicals & Plastics Technology Corporation | Process for production of homogeneous polyethylene |
| US6300451B1 (en) * | 1994-10-24 | 2001-10-09 | Exxon Chemical Patents Inc. | Long-chain branched polymers and their production |
| US5670595A (en) * | 1995-08-28 | 1997-09-23 | Exxon Chemical Patents Inc. | Diene modified polymers |
| US5814714A (en) | 1995-11-30 | 1998-09-29 | The Dow Chemical Company | Mono-olefin/polyene interpolymers, method of preparation, compositions containing the same, and articles made thereof |
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| JP2003520870A (ja) | 2003-07-08 |
| WO2001053364A1 (en) | 2001-07-26 |
| US6509431B1 (en) | 2003-01-21 |
| EP1261651A1 (en) | 2002-12-04 |
| KR20020091084A (ko) | 2002-12-05 |
| BR0107651A (pt) | 2002-10-15 |
| CA2397639A1 (en) | 2001-07-26 |
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