JP2011046953A - ポリブテン−1(共)重合体およびそれらの製造方法 - Google Patents
ポリブテン−1(共)重合体およびそれらの製造方法 Download PDFInfo
- Publication number
- JP2011046953A JP2011046953A JP2010226881A JP2010226881A JP2011046953A JP 2011046953 A JP2011046953 A JP 2011046953A JP 2010226881 A JP2010226881 A JP 2010226881A JP 2010226881 A JP2010226881 A JP 2010226881A JP 2011046953 A JP2011046953 A JP 2011046953A
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- Prior art keywords
- polybutene
- copolymer
- homopolymer
- compound
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001748 polybutylene Polymers 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 30
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229920001519 homopolymer Polymers 0.000 claims abstract description 9
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 239000004711 α-olefin Substances 0.000 claims abstract description 7
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 4
- 238000004458 analytical method Methods 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 39
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- -1 ethylene, propylene Chemical group 0.000 claims description 12
- 239000000499 gel Substances 0.000 claims description 10
- 229920001083 polybutene Polymers 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011949 solid catalyst Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- 230000000707 stereoselective effect Effects 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 24
- 239000010936 titanium Substances 0.000 description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000002083 X-ray spectrum Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- PPQUYYAZSOKTQD-UHFFFAOYSA-M diethylalumanylium;iodide Chemical compound CC[Al](I)CC PPQUYYAZSOKTQD-UHFFFAOYSA-M 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VFIOZKTXVHLWRA-UHFFFAOYSA-N (2-ethylpiperidin-1-yl)-dimethoxy-(1,1,1-trifluoropropan-2-yl)silane Chemical compound CCC1CCCCN1[Si](OC)(OC)C(C)C(F)(F)F VFIOZKTXVHLWRA-UHFFFAOYSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 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
- 239000003755 preservative agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXLWJGIPGJFBEZ-UHFFFAOYSA-N tert-butyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(C)(C)C HXLWJGIPGJFBEZ-UHFFFAOYSA-N 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004846 x-ray emission Methods 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
-
- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium 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
- C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
- C08F4/6465—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64 containing silicium
-
- 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
- C08F4/651—Pretreating with non-metals or metal-free compounds
-
- 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
-
- 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
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/901—Monomer polymerized in vapor state in presence of transition metal containing catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/902—Monomer polymerized in bulk in presence of transition metal containing catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
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Abstract
【解決手段】以下の特性を有するポリブテン−1単独重合体、またはブテン−1のほかに2〜10の炭素原子を有するアルファ−オレフィンを20重量%まで含む共重合体。:(i)特定の方法に従ったNMR分析により測定されたアイソタクチックインデックス(mmmm%)が93より高く;(ii)特定の方法に従ったGPC分析により測定された分子量分布(MWD)がMw/Mnで6より高く;そして(iii)Tiで表わされる触媒残渣の含量が50ppmより低い。
【選択図】なし
Description
驚くべきことに、非常に高い結晶化度および広い分子量分布を有するポリブテン−1(共)重合体が、上記の要求に合うことが見出された。したがって、以下の性質で特徴付けられるポリブテン−1単独重合体またはブテン−1以外の2〜10の炭素原子を有するアルファーオレフィンを20重量%まで含むポリブテン−1共重合体を提供することが本発明の目的である。
(i)後記の方法によるNMR分析で測定されるアイソタクチック指数(mmmm%)が93よりも高く;
(ii)後記の方法によるGPC分析で測定される分子量分布(MWD)がMw/Mnで6より高く;そして(iii)Tippmで表わされる触媒残渣の含量が50よりも低い。
アルキル−Al化合物(B)は、好ましくは、例えば、トリエチルアルミニウム、トリイソブチルアルミニウム、トリ−n−ブチルアルミニウム、トリ−n−ヘキシルアルミニウム、トリ−n−オクチルアルミニウムのようなトリアルキルアルミニウム化合物の中から選択される。トリアルキルアルミニウムのアルキルアルミニウムハライド、アルキルアルミニウムハイドライドまたはAlEt2ClおよびAl2Et3Cl3のようなアルキルアルミニウムセスキクロライドとの混合物を用いることも可能である。
適当な外部電子供与化合物は、シリコン化合物、エーテル類、エステル類、アミン類、複素環化合物類、特に2,2,6,6−テトラメチルピペリジン、ケトン類および一般式(I)の1,3−ジエーテル類を含む。;
特性
<13CNMRによるアイソタクチックインデックス(mmmm%)の決定>
この測定は、C2Cl4D2中の重合体の10重量%溶液を製造し、FTモードにおいてウォルツ16デカップリングプロトン下125.7MHzで、スペクトラル幅10Khzで、90°パルス角度およびパルス反復16秒および3600スキャンで操作するDRX500MHz器を用いて、120℃でスペクトルを記録することにより行われる。アイソタクチックインデックスは、次いで、「化学シフト計算および重合機構から決定された5重合体の炭素−13 NMRスペクトルの帰属、T.アサクラほか、Macromolecules 1991,242334−2340に基づいて計算される。
ASTMD1238 条件“E”
<ゲル透過クロマトグラフィー(GPC)によるMWDの決定>
TSKカラムセット(GMHXL−HT型)を備えたウォーターズ150−C ALC/GPCシステムを用いて、135℃で、溶媒として1,2−ジクロロベンゼン(ODCB)(2,6−ジ−t−ブチル p−クレゾール(BHT)0.1 vol.で安定化された)を用い、流速1ml/分で作動させて、これを決定する。
10Mpaの荷重下、50℃の温度で、10000分間保った試料の変形%を測定することにより評価した。
ISO1167:1996により求めた。
<コモノマー含量>
NMR分光法により決定したコモノマーの重量%である。
ASTM2857−70
触媒井渣(ppm Ti)
重合体中のチタンのppmはPhillips PW1404器具を用いたX−線蛍光分光法により測定する。
m2当たりのゲルの数の決定は、プロジェクターにより拡大スケールで壁面グラフ上に投影されたポリブテンフィルム(50μ厚さ、130×7.5cmサイズ)の一片のゲルの数を目視により検出することにより行う。計数は、同じフィルムの5つの異なった片について行い、最終的な数はNo=A/Sで表わす。ここで、Noはm2当たりのゲルの数であり、Aは5つのフィルム片において数えられたグルの数であり、Sは検査された5つのフィルム片のm2で表わした全表面である。
<破断強さ> ASTM D 638
<降伏伸び> ASTM D 638
<破断伸び> ASTM D 638
<曲げ弾性率> ASTM D 790
<引張弾性率> ASTM D 790
<アイゾッド> ASTM D 256
<固体触媒成分の製造>
窒素置換された500mlの4つ口丸底フラスコにTiCl4225mlを0℃で入れた。攪拌している間に微小球体状のMgCl2・2.1C2H5OH(10,000rpmに代えて3,000rpmで操作した以外は、USP4,399,054の実施例2に記載のようにして製造された付加物の一部熱脱アルコールにより得られた)10.3gを加えた。フラスコを40℃に加熱し、ジイソブチルフタレート6.5ミリモルをその上に加えた。温度を100℃に上げ、2時間維持した。次いで、攪拌を止め、固体生成物を安定させ、上澄液を吸い取った。
上記のようにして製造された触媒成分、AlEt3(TEA)と、TEA/触媒重量比10、TAE/DIPMS重量比8およびDIPMS/触媒 重量比1.25を有するような量のジイソプロピルジメトキシシラン(DIPMS)とを、不活性媒体としてプロパンを含む活性化容器中、室温で混合し、約15分間滞留させた。
このようにして得られた生成物を、次いで以下の条件で作動する第2気相重合反応器に入れた。
重合時間(時間):9
圧力(bar):9
ブテン(気相中のモル%):20
プロパン(気相中のモル%):80
水素(g/h):6.7
収量:5Kg/g触媒
以下の特性を有するポリブテン−1最終生成物を得た。
MWD:10.3
Mw:740000
Mn:71800
MIE(g/10分):0.48
触媒残渣(Ti ppm):27
ポリプロピレン含量(重量%):5
得られたポリブテンを以下の性質の測定に供した。
<ブテン−1の塊重合>
上記のようにして製造された触媒成分、AliBu3(TIBA)と、TIBA/触媒の重量比80、TIBA/DIPMS重量比10を有するような量のジイソプロピルジメトキシシランとを、不活性媒体としてヘキサンを含む活性化容器中、室温で混合し、約5分間滞留させた。
重合時間(時間):2時間
圧力(bar):10
次いで、水素を反応器に入れ、第2重合工程を以下の条件で行った。
重合時間(時間):2
圧力(bar):14
達成された収量:14Kg/g触媒
以下の特性を有するポリブテン−1最終生成物を得た。
MWD:8
MIE(g/10分):0.35
触媒残渣(Ti ppm):2
得られたポリブテンについて行った試験の結果を表1に示す。
Claims (27)
- 以下の特性:
(i)特定の方法に従ったNMR分析により測定されたアイソタクチックインデックス(mmmm%)が93よりも高く;
(ii)特定の方法に従ったGPC分析により測定された分子量分布(MWD)がMw/Mnで6より高く;そして
(iii)触媒残渣の含量がTi ppmで50よりも低いポリブテン−1単独重合体、またはブテン−1のほかに2〜10の炭素原子を有するアルファ−オレフィンを20重量%まで含むポリブテン−1共重合体。 - アイソタクチックインデックスが94よりも高い請求項1のポリブテン−1単独または共重合体。
- アイソタクチックインデックスが95よりも高い請求項2のポリブテン−1単独または共重合体。
- MWDが7よりも高い請求項1のポリブテン−1単独または共重合体。
- MWDが9よりも高い請求項4のポリブテン−1単独または共重合体。
- アイソタクチックインデックスが95よりも高い請求項5のポリブテン−1単独は共重合体。
- アルファ−オレフィンが、エチレン、プロピレンおよびヘキセン−1からなる群より選択される請求項1のポリブテン−1共重合体。
- 該オレフィンの含量が2〜15重量%である請求項7のポリブテン−1共重合体。
- 該オレフィンの含量が5〜10重量%である請求項8のポリブテン−1共重合体。
- さらに好ましくは10〜0.1の範囲からなるMIEを有する請求項9のポリブテン−1単独または共重合体。
- MIEが、1〜0.1、特に0.3〜0.5の範囲からなるMIEを有する請求項10のポリブテン−1単独または共重合体。
- ポリプロピレンを0.5〜20重量%含む請求項1〜11のいずれかのポリブテン−1単独または共重合体。
- ポリプロピレンを1〜10重量%含む請求項12のポリブテン−1単独または共重合体。
- 2形態のMWDを有する請求項1〜13のいずれかのポリブテン−1単独または共重合体。
- m2当たりゲルの数が400より低い請求項1〜14のいずれかのポリブテン−1単独または共重合体。
- m2当たりゲルの数が300より低い請求項15のポリブテン−1単独または共重合体。
- m2当たりゲルの数が200より低い請求項16のポリブテン−1単独または共重合体。
- 請求項1〜17のいずれかのポリブテンから製造された物品。
- (A)Ti化合物およびMgCl2に担持された内部電子供与化合物からなる固体成分;
(B)アルキルアルミニウム化合物および
(C)外部電子供与化合物からなる立体特異性触媒の存在下に行われる請求項1〜17のいずれかポリブテン−1単独または共重合体の製造方法。 - 外部電子供与化合物(C)がジイソプロピルジメトキシシランである請求項19の製造方法。
- 内部電子供与化合物がジイソブチルフタレートである請求項20の製造方法。
- 気相中で行われる請求項19〜21のいずれかの製造方法。
- 溶液中で行われる請求項19〜21のいずれかの製造方法。
- 液体モノマー中で行われる請求項23の製造方法。
- 予備重合工程が、第1主重合工程の前に行われる請求項19〜24のいずれかの製造方法。
- 予備重合工程が、固体触媒成分g当たり0.5〜2000gの量のプロピレンの重合により行われる請求項25の製造方法。
- 異なった作動条件で操作される少なくとも2つの重合反応器中で行われる請求項19〜26のいずれかの製造方法。
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CN111087503B (zh) * | 2018-10-23 | 2023-03-14 | 中国石油化工股份有限公司 | 1-丁烯聚合物及1-丁烯淤浆聚合方法 |
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JP2019123842A (ja) * | 2018-01-19 | 2019-07-25 | 三井化学株式会社 | 樹脂組成物およびその用途 |
JP7044565B2 (ja) | 2018-01-19 | 2022-03-30 | 三井化学株式会社 | 樹脂組成物およびその用途 |
Also Published As
Publication number | Publication date |
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CA2289026A1 (en) | 1999-09-10 |
TR199902698T1 (xx) | 2000-10-23 |
US6306996B1 (en) | 2001-10-23 |
ES2205795T3 (es) | 2004-05-01 |
AR018315A1 (es) | 2001-11-14 |
RU2219190C2 (ru) | 2003-12-20 |
NO995386L (no) | 1999-11-04 |
NO995386D0 (no) | 1999-11-04 |
KR100598444B1 (ko) | 2006-07-10 |
ID23020A (id) | 1999-12-30 |
BR9904849A (pt) | 2000-07-25 |
JP5933170B2 (ja) | 2016-06-08 |
CN1256698A (zh) | 2000-06-14 |
AU744327B2 (en) | 2002-02-21 |
KR20010012216A (ko) | 2001-02-15 |
BR9904849B1 (pt) | 2009-01-13 |
EP0980396B1 (en) | 2003-08-20 |
ES2205795T5 (es) | 2009-11-24 |
WO1999045043A1 (en) | 1999-09-10 |
EP0980396B2 (en) | 2009-08-19 |
JP2001523302A (ja) | 2001-11-20 |
CA2289026C (en) | 2008-11-18 |
EP0980396A1 (en) | 2000-02-23 |
TW553953B (en) | 2003-09-21 |
AU3143199A (en) | 1999-09-20 |
DE69910511D1 (de) | 2003-09-25 |
CN1140545C (zh) | 2004-03-03 |
DE69910511T2 (de) | 2004-06-17 |
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