JP7498761B2 - 超高分子量ポリエチレンの重合方法及びその触媒の製造方法 - Google Patents
超高分子量ポリエチレンの重合方法及びその触媒の製造方法 Download PDFInfo
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims description 59
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims description 59
- 239000003054 catalyst Substances 0.000 title claims description 44
- 238000000034 method Methods 0.000 title claims description 29
- 230000000379 polymerizing effect Effects 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title description 12
- -1 organosilane compound Chemical class 0.000 claims description 35
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 235000011147 magnesium chloride Nutrition 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 9
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 9
- 150000002681 magnesium compounds Chemical class 0.000 claims description 8
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000002245 particle Substances 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000004907 flux Effects 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001282 organosilanes Chemical class 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 230000037048 polymerization activity Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000006749 (C6-C60) aryl group Chemical group 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical group [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910052805 deuterium Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001296 polysiloxane Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- MNCMBBIFTVWHIP-UHFFFAOYSA-N 1-anthracen-9-yl-2,2,2-trifluoroethanone Chemical group C1=CC=C2C(C(=O)C(F)(F)F)=C(C=CC=C3)C3=CC2=C1 MNCMBBIFTVWHIP-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005018 aryl alkenyl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
- C08F4/652—Pretreating with metals or metal-containing compounds
- C08F4/654—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof
- C08F4/6543—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium
- C08F4/6545—Pretreating with metals or metal-containing compounds with magnesium or compounds thereof halides of magnesium and metals of C08F4/64 or compounds thereof
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- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- 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
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- 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
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- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/01—High molecular weight, e.g. >800,000 Da.
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/18—Bulk density
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/24—Polymer with special particle form or size
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
R1OOCR2COOR3 (1)
前記式(1)において、R1、R3は炭素原子1ないし10個の線状または分岐状アルキル基であり、R2は炭素原子1~20個の炭化水素である。
前記式(2)において、R4及びR5、R6、R7はそれぞれ独立に、線状、分岐状及び環状炭素原子1~20個のアルキル基、炭素原子1~20個のアルコキシ基、炭素原子6~60個のアリール基及びヘテロ原子を含む炭素原子1~20個のアルキル基である。
(超高分子量ポリエチレン製造用の固体触媒の製造)
第1段階:マグネシウムハライドアルコール付加物(adduct)溶液の製造
機械式攪拌機が設けられた1L反応器を窒素雰囲気に置換した後、固体二塩化マグネシウム(MgCl2)20g、トルエン200ml、ノマルブタノール120mlを投入し、350rpmで攪拌した。温度を1時間の間65℃に昇温した後、2時間保持して溶媒によく溶けた均一なマグネシウムハライドアルコール付加物溶液を得た。
第1段階において製造された溶液の温度を20℃に冷却した後、TiCl420mlを40分間ゆっくり仕込んだ(0.5ml/min)。その後、TiCl462.5mlを100分間より速く仕込んだ(0.625ml/min)。この際、反応器の温度が25℃以上に上昇しないように注意して温度を保持した。
仕込みが完了したら、反応器の温度を1時間の間60℃に昇温し、さらに1時間保持した。
全ての過程が完了すると反応器を静置して固体成分を完全に沈め、上澄液を除去した後、反応器内の固体成分を300mlのトルエンで1回洗浄及び沈殿させ、液状の不純物を完全に除去し、清浄な塩化マグネシウム担体を固体として得た。
前記塩化マグネシウム担体にトルエン200mlを仕込み、250rpmで撹拌しながら25℃を保持した。その後、TiCl430mlを一度に仕込み、1時間の間保持して一次反応させた。その後、ジメチルフタレート(dimethyl phthalate)2mlを仕込んだ後、反応器温度を60℃に昇温した後、1時間保持してTiCl4と担体との間の二次反応を行った。
全ての過程が完了すると反応器を静置して固体成分を完全に沈めた後、上澄液を除去した。製造された固体触媒はトルエン200mlで1回、ヘキサン200mlで6回洗浄及び沈殿して不純物を除去した。
4リットル容量の連続式重合反応器にエチレンを連続的に流し込み、内部をエチレンで満たした。トリイソブチルアルミニウム0.5M、トリエチルアルミニウム0.5Mとなるように有機アルミニウム混合物のヘキサン希釈液を調製した。チタニウム1.0Mの触媒ヘキサン希釈液、有機シラン1.0M希釈液をそれぞれ別のタンクに調製した。
反応器温度を80℃に保持しながら有機アルミニウム希釈液、触媒希釈液、有機シラン希釈液をTi:TEAl:TIBA:Si=1:0.5:0.5:5となるように一定の速度で仕込んだ。反応器内のヘキサンスラリーが計2リットルになるように持続的にヘキサンを仕込んだ。反応器の内圧は5Kg/cm2G、滞留時間を2時間に保持した。反応器から排出されたヘキサンスラリーをフィルター及び乾燥して超高分子量ポリエチレン粒子を得た。
実施例1から重合時のトリイソブチルアルミニウムを0.25ミリモル、トリエチルアルミニウムを0.75ミリモルに変更したことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
実施例1から重合時のトリイソブチルアルミニウムを0.75ミリモル、トリエチルアルミニウムを0.25ミリモルに変更したことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
実施例1から重合時のトリイソブチルアルミニウムを1ミリモル、トリエチルアルミニウムを1ミリモルに変更したことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
実施例1から重合時のトリイソブチルアルミニウムを0.25ミリモル、トリエチルアルミニウムを0.25ミリモルに変更したことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
実施例1から重合時のトリイソブチルアルミニウムを0ミリモル、トリエチルアルミニウムを1ミリモルに変更したことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
実施例1から重合時のトリイソブチルアルミニウムを1ミリモル、トリエチルアルミニウムを0ミリモルに変更したことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
実施例1から重合時のジシクロペンチルジメトキシシランを投入していないことを除き、実施例1と同様の方法で超高分子量ポリエチレンを製造した。
前述の実施例1ないし5及び比較例1ないし3をトリイソブチルアルミニウム及びトリエチルアルミニウムの含量を基準としてまとめると、下記表1のとおりである。
前述の実施例1ないし5及び比較例1ないし3により製造された超高分子量ポリエチレン重合体の物性を測定した結果は表2のとおりであった。
重合活性(kg-PE/g-触媒)は、用いた触媒量当たりに生成された重合体の重量比で計算した。
ASTM D1895-96にしたがって測定した。
重合体の分子量(Mv)は固有粘度を測定し、マーゴリーズの方程式を介して計算した。
具体的には、分子量(MW)をASTM D 4020にしたがい固有粘度[η]から算出した。高分子の場合、希薄濃度の溶液上で粘度が有用な情報を提供することができ、高分子の粘度を溶液の粘度と濃度で割った値を比粘度(specific viscosity)とし、高分子の濃度が0になるとき比粘度の外挿値を固有粘度(Intrinsic Viscosity、IV)と定義する。直鎖状の高分子は、IV値が高分子のサイズに主に影響されるため、分子量と高い相関性を有し、超高分子量ポリエチレンの場合にはマーゴリーズの方程式(Margoliesequation)が広く用いられている。
Mw=5.37×104×[η]1.49
Mw=average molecular weight(g/mol)
[η]=intrinsic viscosity(dl/g)
重合体の粒子サイズの分布図は、レーザ粒子分析器(Mastersizer X、Malvern Instruments)を用いて測定し、結果は平均粒子サイズはD(v,0.5)、粒子サイズ分布は(D(v,0.9)-D(v,0.1))/D(v,0.5)で示した。
ここで、D(v,0.5)はサンプルに含まれた粒子のサイズの中間値を表し、D(v,0.9)とD(v,0.1)はそれぞれサイズ分布基準90%と10%に位置する粒子サイズを意味する。粒子サイズ分布の数が小さいほど粒子サイズ分布が狭いことを意味する。
重合体の粒子束は、1μmの孔を有する金属篩を用いて総重量に対して固まった粒子の量を測定した。
Claims (8)
- チタニウム活性点を含有する主触媒、トリエチルアルミニウム及びトリイソブチルアルミニウムを混合した有機アルミニウム助触媒並びに有機シラン化合物を反応して超高分子量ポリエチレンを重合する超高分子量ポリエチレンの重合方法。
- 前記主触媒は、二塩化マグネシウム(MgCl2)にチタニウムが担持されたチーグラー・ナッタ系触媒である請求項1に記載の超高分子量ポリエチレンの重合方法。
- 前記主触媒は下記の方法で製造される請求項2に記載の超高分子量ポリエチレンの重合方法:
前記二塩化マグネシウム(MgCl2)をアルコールと反応させてマグネシウム化合物溶液を製造する第1段階;
前記マグネシウム化合物溶液に四塩化チタニウムと反応させて前駆体を製造する第2段階;及び
前記前駆体を四塩化チタニウムと1次反応後、下記式(1)で表されるジエステル化合物と反応させて触媒を製造する第3段階、
R1OOCR2COOR3 (1)
前記式(1)において、R1、R3は炭素原子1ないし10個の線状または分岐状アルキル基であり、R2は炭素原子1~20個の炭化水素である。 - 前記超高分子量ポリエチレンを重合する際に用いる溶媒は、線状、分岐状及び環状のいずれかの飽和炭化水素である請求項1に記載の超高分子量ポリエチレンの重合方法。
- 前記有機アルミニウム助触媒の量は、前記主触媒のチタニウム原子のモル当たり前記助触媒のアルミニウム原子のモルが0.1から100である請求項1に記載の超高分子量ポリエチレンの重合方法。
- 前記有機シラン化合物の量は、前記主触媒のチタニウム原子のモル当たり0.2~50モルである請求項6に記載の超高分子量ポリエチレンの重合方法。
- 前記超高分子量ポリエチレンを重合する際の重合反応は1~60Kg/cm2Gの圧力条件、60~95℃の温度条件下で反応物の滞留時間が1から4時間の間行われる請求項1に記載の超高分子量ポリエチレンの重合方法。
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