JP2005533138A - 高い透明性を有する柔軟なプロピレンコポリマー組成物 - Google Patents
高い透明性を有する柔軟なプロピレンコポリマー組成物 Download PDFInfo
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- JP2005533138A JP2005533138A JP2004513350A JP2004513350A JP2005533138A JP 2005533138 A JP2005533138 A JP 2005533138A JP 2004513350 A JP2004513350 A JP 2004513350A JP 2004513350 A JP2004513350 A JP 2004513350A JP 2005533138 A JP2005533138 A JP 2005533138A
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- Prior art keywords
- propylene copolymer
- propylene
- group
- alkyl
- copolymer composition
- 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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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 227
- 229920001577 copolymer Polymers 0.000 title claims abstract description 199
- 239000000203 mixture Substances 0.000 title claims abstract description 109
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 36
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 30
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 230000000737 periodic effect Effects 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000005842 heteroatom Chemical group 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000002195 soluble material Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000002667 nucleating agent Substances 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052719 titanium Chemical group 0.000 claims description 3
- 239000010936 titanium Chemical group 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002076 thermal analysis method Methods 0.000 claims description 2
- -1 aluminum tert-butylbenzoate Chemical compound 0.000 description 38
- 238000012360 testing method Methods 0.000 description 23
- 229920000642 polymer Polymers 0.000 description 20
- 229920001155 polypropylene Polymers 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 14
- 230000007704 transition Effects 0.000 description 13
- 230000002087 whitening effect Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002841 Lewis acid Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000008040 ionic compounds Chemical class 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 239000012968 metallocene catalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 4
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 4
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 4
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 125000003106 haloaryl group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 2
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical class [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 125000001188 haloalkyl group Chemical group 0.000 description 2
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- 238000001746 injection moulding Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- CHMCAIRITMOPFF-CGXNFDGLSA-N (3R,4S,5R,6S)-3-methyl-1,8-diphenylocta-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C[C@@](C(O)=CC1=CC=CC=C1)(O)[C@@H](O)[C@H](O)[C@H](O)C(O)=CC1=CC=CC=C1 CHMCAIRITMOPFF-CGXNFDGLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- BKWNZVQQIYSORG-UHFFFAOYSA-N 3-ethylbicyclo[2.2.1]hepta-1,3-diene Chemical compound C1CC2=CC(CC)=C1C2 BKWNZVQQIYSORG-UHFFFAOYSA-N 0.000 description 1
- RMDKEBZUCHXUER-UHFFFAOYSA-N 4-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C)C2 RMDKEBZUCHXUER-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RGPSRYWDFHAWOT-UHFFFAOYSA-N CCCCCCCC[Mg]CCCC Chemical compound CCCCCCCC[Mg]CCCC RGPSRYWDFHAWOT-UHFFFAOYSA-N 0.000 description 1
- NTWHKVMZCKIKOK-UHFFFAOYSA-N CCCCCCC[Mg]CCCC Chemical compound CCCCCCC[Mg]CCCC NTWHKVMZCKIKOK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 241000408710 Hansa Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
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- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052795 boron group element Inorganic materials 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 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 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical group OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
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- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
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- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000003136 n-heptyl 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])* 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
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
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- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 150000003254 radicals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229940054334 silver cation Drugs 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
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- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
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Abstract
Description
A)1〜20重量%のプロピレン以外のオレフィンを含有するプロピレンコポリマーおよび
B)5〜98重量%のプロピレン以外のオレフィンを含有する少なくとも1つのプロピレンコポリマー
を含み、メタロセン化合物をベースにする触媒系を用いる2段階または多段階の重合により得ることができ、触媒系が両段階で使用される、プロピレンコポリマー組成物によって達成されることを見出した。
Mは、ジルコニウム、ハフニウムまたはチタニウム、好ましくはジルコニウムであり、
2つの基Xはまた、互いに結合して、好ましくはC4〜C40−ジエニル配位子、特に1,3−ジエニル配位子、または−OR’O−基(式中、置換基R’は、C1〜C40−アルキリデン、C6〜C40−アリーリデン、C7〜C40−アルキルアリーリデンおよびC7〜C40−アリールアルキリデンからなる基より選択される二価の基である)を形成してもよく、
Xは好ましくはハロゲン原子または−Rもしくは−OR基であるか、または2つの基Xが−OR’O−基を形成し、Xは特に好ましくは塩素またはメチルであり、
Lは、好ましくは、−SiMe2−、−SiPh2−、−SiPhMe−、−SiMe(SiMe3)−、−CH2−、−(CH2)2−、−(CH2)3−および−C(CH3)2−からなる群より選択される基であり、
R1は、好ましくはα位で分枝しておらず、好ましくはα位で分枝しない直鎖または分枝鎖のC1〜C10−アルキル基、特にメチル、エチル、n−プロピルまたはn−ブチルのような直鎖のC1〜C4−アルキル基であり、
R3は、同一または異なって、それぞれが互いに独立して、元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであり、あるいは2つの基R3が結合して飽和または不飽和のC3〜C20−環を形成してもよく、
R3は、好ましくは直鎖または分枝鎖のC1〜C10−アルキル基であり、かつ
の基であり、
記号*および**で示した原子は、同じ記号で示した式(I)の化合物の原子と結合し、かつ
R5は、好ましくは水素または直鎖もしくは分枝鎖のC1〜C10−アルキル基、特にメチル、エチル、n−プロピルまたはn−ブチルのような直鎖のC1〜C4−アルキル基であり、かつ
R7は、同一または異なって、それぞれが互いに独立して、水素またはハロゲンまたは元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであって、あるいは2つの基R7が結合して飽和または不飽和のC3〜C20環を形成してもよく、
R7は、好ましくは水素原子であり、かつ
R8は、好ましくは式−C(R9)3:
の分枝鎖アルキル基である)
のアリール基である)
の二価基である]
のメタロセン化合物をベースとする触媒系が特に好ましい。
ジメチルシランジイル(2−エチル−4−(4’−tert−ブチルフェニル)インデニル)(2−イソプロピル−4−(4’’−tert−ブチルフェニル)インデニル)ジルコニウムジクロリド、
ジメチルシランジイル(2−メチル−4−(4’−tert−ブチルフェニル)インデニル)(2−イソプロピル−4−(1−ナフチル)インデニル)−ジルコニウムジクロリド、
ジメチルシランジイル(2−メチル−4−フェニル−1−インデニル)(2−イソプロピル−4−(4’−tert−ブチルフェニル)−1−インデニル)−ジルコニウムジクロリド、
ジメチルシランジイル(2−メチルチアペンテニル)(2−イソプロピル−4−(4’−tert−ブチルフェニル)インデニル)ジルコニウムジクロリド、
ジメチルシランジイル(2−イソプロピル−4−(4’−tert−ブチルフェニル)インデニル)(2−メチル−4,5−ベンズインデニル)ジルコニウムジクロリド、
ジメチルシランジイル(2−メチル−4−(4’−tert−ブチルフェニル)インデニル)(2−イソプロピル−4−(4’−tert−ブチルフェニル)インデニル)ジルコニウムジクロリド、
ジメチルシランジイル(2−メチル−4−(4’−tert−ブチルフェニル)インデニル)(2−イソプロピル−4−フェニルインデニル)ジルコニウムジクロリド、
ジメチルシランジイル(2−エチル−4−(4’−tert−ブチルフェニル)インデニル)(2−イソプロピル−4−フェニル)インデニル)ジルコニウムジクロリド、および
ジメチルシランジイル(2−イソプロピル−4−(4’−tert−ブチルフェニル)インデニル)(2−メチル−4−(1−ナフチル)インデニル)−ジルコニウムジクロリド、
ならびにそれらの混合物である。
R21は、C1〜C4−アルキル基、好ましくはメチルまたはエチル基であり、かつ
mは、5〜30、好ましくは10〜25の整数である)
の開鎖または環状のアルミノキサン化合物である。
M2X1X2X3 (XI)
M2は、元素の周期表の13族の元素、特にB、AlまたはG、好ましくはBであり、
X1、X2およびX3はそれぞれ、水素、C1〜C10−アルキル、C6〜C15−アリール、アルキルアリール、アリールアルキル、ハロアルキルもしくはハロアリール(それぞれアルキル基に1〜10個の炭素原子を有し、アリール基に6〜20個の炭素原子を有する)、またはフッ素、塩素、臭素もしくはヨウ素であり、特にハロアリール、好ましくはペンタフルオロフェニルである)
の化合物が好ましい。
X1、X2およびX3が同じであり、好ましくはトリス(ペンタフルオロフェニル)ボランである式(XI)の化合物が特に好ましい。
[(Ya+)Q1Q2...Qz]d+ (XII)
Yは、元素の周期表の1〜16族の元素であり、
Q1〜Qzは、C1〜C28−アルキル、C6〜C15−アリール、アルキルアリール、アリールアルキル、ハロアルキル、ハロアリール(それぞれアリール基に6〜20個の炭素原子を有し、アルキル基に1〜28個の炭素原子を有する)、C3〜C10−シクロアルキル(C1〜C10−アルキル基で置換されてもよい)、またはハロゲン、C1〜C28−アルコキシ、C6〜C15−アリールオキシ、シリルもしくはメルカプト基のような1価の負に荷電した基であり、
zは0〜5の整数であり、
dは差a−zであるが、dは1以上である)
のカチオンの塩様化合物を含む。
M3(R22)r(R23)s(R24)t (XIII)
M3は、アルカリ金属、アルカリ土類金属または周期表の13族の金属、すなわちホウ素、アルミニウム、ガリウム、インジウムまたはタリウムであり、
sおよびtは、0〜2の整数であり、総和r+s+tはM3の原子価に対応する)
の金属化合物をさらに含むことができ、
ここで、式(XIII)の金属化合物はカチオン生成化合物と同一ではなく、式(XIII)の種々の金属化合物の混合物を使用することも可能である)
M3がリチウム、マグネシウムまたはアルミニウムであり、かつ
R23およびR24がそれぞれC1〜C10−アルキルである
ものが好ましい。
メタロセン触媒の調製
3kgのサイロポール(Sylopol)948を、フィルタープレートが下向きのプロセスフィルター中に置き、そして15Lのトルエンに懸濁した。7Lの30重量%強度のMAO溶液(Albemarle製)を、内部温度が35℃を超えない速度で撹拌しながら計量投入した。低スターラー速度でさらに1時間撹拌後、最初は加圧せずに、次いで3barの窒素圧下で、懸濁物を濾過した。担体材料の処理と並行して、2.0Lの30重量%強度のMAO溶液を、反応容器中に置き、92.3gのrac−ジメチルシリル(2−メチル−4−(パラ−tert−ブチルフェニル)インデニル)(2−イソプロピル−4−(パラ−tert−ブチルフェニル)インデニル)ジルコニウムジクロライドを添加し、溶液を1時間撹拌し、さらに30分間静置した。続いて、出口を塞ぎ、前処理した担体材料上に溶液を流した。付加が完了した後、出口を開き、濾液を流し出した。続いて、出口を閉じ、濾塊を15分間撹拌し、1時間静置した。次いで、出口を開いて、3barの窒素圧を用いて、濾塊から液体を圧出した。15Lのイソドデカンを残った固形物に添加し、混合物を15分間撹拌し、濾過した。洗浄工程を繰り返し、続いて濾塊を3barの窒素圧を用いて加圧乾燥させた。重合での使用のため、触媒の全量を15Lのイソドデカン中に再懸濁した。
直列に接続されそれぞれが200Lの利用可能な容積を有しそして自立型ヘリカルスターラー(helical stirrer)を備えた2つの撹拌オートクレーブ中で、このプロセスを行った。両方の反応器とも、微細に分割されたプロピレンポリマーの撹拌固定床(agitated fixed bed)を含んでいた。
用途関連試験に必要な試験片の製造および検査自体は、表3に示した規格に従って行なった。
Claims (16)
- A)1〜20重量%のプロピレン以外のオレフィンを含有するプロピレンコポリマーおよび
B)5〜98重量%のプロピレン以外のオレフィンを含有する少なくとも1つのプロピレンコポリマー
を含み、メタロセン化合物をベースにする触媒系を用いる2段階または多段階の重合により得ることができ、触媒系が両段階で使用される、プロピレンコポリマー組成物。 - 50,000g/mol〜500,000g/molの範囲の数平均モル質量Mnを有する請求項1に記載のプロピレンコポリマー組成物。
- 触媒系が、少なくとも1つの式(I):
Mは、ジルコニウム、ハフニウムまたはチタニウムであり、
Xは、同一または異なって、それぞれが互いに独立して、水素またはハロゲンまたは−R、−OR、−OSO2CF3、−OCOR、−SR、−NR2もしくは−PR2基(式中、Rは、元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであって、2つの基Xはまた、互いに結合していてもよく、
Lは、元素の周期表の13〜17族のヘテロ原子を含んでいてもよい、C1〜C20−アルキリデン基、C3〜C20−シクロアルキリデン基、C6〜C20−アリーリデン基、C7〜C20−アルキルアリーリデン基およびC7〜C20−アリールアルキリデン基からなる群より選択される二価の橋架基であるか、あるいは5個までのケイ素原子を有するシリリデン基、例えば−SiMe2−または−SiPh2−であり、
R1は、元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであって、
R1は、好ましくはα位で分枝しない直鎖または分枝鎖のC1〜C10−アルキル基、特にメチル、エチル、n−プロピルまたはn−ブチルのような直鎖のC1〜C4−アルキル基であり、
R2は、式−C(R3)2R4:
(式中、
R3は、同一または異なって、それぞれが互いに独立して、元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであり、あるいは2つの基R3が結合して飽和または不飽和のC3〜C20−環を形成してもよく、
R4は、水素または元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルである)
の基であり、
TおよびT’は、式(II)、(III)、(IV)、(V)または(VI):
記号*および**で示した原子は、同じ記号で示した式(I)の化合物の原子と結合し、かつ
R5は、同一または異なって、それぞれが互いに独立して、水素またはハロゲンまたは元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであり、
R6は、同一または異なって、それぞれが互いに独立して、ハロゲンまたは元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルである)
の二価基である]
のメタロセン化合物を含む請求項1または2に記載のプロピレンコポリマー組成物。 - R6が、式(VII):
R7は、同一または異なって、それぞれが互いに独立して、水素またはハロゲンまたは元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルであって、あるいは2つの基R7が結合して飽和または不飽和のC3〜C20環を形成してもよく、
R8は、水素またはハロゲンまたは元素の周期表の13〜17族の1以上のヘテロ原子または1以上の不飽和結合を含んでいてもよい、直鎖または分枝鎖のC1〜C20−アルキル、1以上のC1〜C10−アルキル基で置換されていてもよいC3〜C20−シクロアルキル、C6〜C20−アリール、C7〜C20−アルキルアリールまたはC7〜C20−アリールアルキルである)
のアリール基である請求項3に記載のプロピレンコポリマー組成物。 - R8が、式−C(R9)3:
(式中、R9は、同一または異なって、それぞれが互いに独立して、直鎖または分枝鎖のC1〜C6−アルキル基であるか、あるいは2または3の基R9が結合して1以上の環系を形成する)
の分枝鎖アルキル基である請求項4に記載のプロピレンコポリマー組成物。 - R1が、α位で分枝していない請求項1〜5のいずれかに記載のプロピレンコポリマー組成物。
- プロピレン以外のオレフィンが、もっぱらエチレンである請求項1〜6のいずれかに記載のプロピレンコポリマー組成物。
- プロピレンコポリマーAとプロピレンコポリマーBとの重量比が、90:10〜80:20の範囲である請求項1〜7のいずれかに記載のプロピレンコポリマー組成物。
- プロピレンコポリマー組成物の総重量に基づいて0.1〜1重量%の核剤を含む請求項1〜8のいずれかに記載のプロピレンコポリマー組成物。
- DMTA(動的機械的熱分析)により決定されるプロピレンコポリマーBのガラス転移温度が、−20℃〜−40℃の範囲である請求項1〜9のいずれかに記載のプロピレンコポリマー組成物。
- モル質量分布Mw/Mnが、1.5〜3.5の範囲である請求項1〜10のいずれかに記載のプロピレンコポリマー組成物。
- A)1〜20重量%のプロピレン以外のオレフィンを含有するプロピレンコポリマーおよび
B)5〜98重量%のプロピレン以外のオレフィンを含有する少なくとも1つのプロピレンコポリマー
を含み、プロピレンコポリマーAおよびプロピレンコポリマーBが分離相として存在し、n−ヘキサン可溶材料の比率が2.6重量%以下(≦2.6)であるプロピレンコポリマー組成物。 - A)1〜20重量%のプロピレン以外のオレフィンを含有するプロピレンコポリマーおよび
B)5〜98重量%のプロピレン以外のオレフィンを含有する少なくとも1つのプロピレンコポリマー
を含み、プロピレンコポリマーAおよびプロピレンコポリマーBが分離相として存在し、かつ30%以下(≦30%)の曇り価を有し、引張弾性率(E)が100〜1500MPaの範囲であるプロピレンコポリマー組成物。 - 2段階重合が実施され、かつメタロセン化合物をベースとする触媒系が使用される請求項1〜11のいずれかに記載のプロピレンコポリマー組成物の製造方法。
- 繊維、フィルムまたは成形品を製造するための請求項1〜13のいずれかに記載のプロピレンコポリマー組成物の使用。
- 請求項1〜13のいずれかに記載のプロピレンコポリマー組成物を、好ましくは実質的な成分として含む繊維、フィルムまたは成形品。
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JP2006316267A (ja) * | 2005-05-10 | 2006-11-24 | Sk Corp | 優れた耐衝撃性、曲げ弾性率および透明性を有するポリプロピレン組成物と該組成物から製造された製品 |
JP2009185259A (ja) * | 2008-02-08 | 2009-08-20 | Japan Polypropylene Corp | プロピレン/エチレン−αオレフィン系ブロック共重合体の製造方法 |
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JP2005529227A (ja) * | 2002-06-12 | 2005-09-29 | バセル ポリオレフィン ジーエムビーエイチ | 良好な低温衝撃靭性と高い透明性を有するプロピレンコポリマー組成物 |
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CN100558807C (zh) * | 2004-03-24 | 2009-11-11 | 巴塞尔聚烯烃股份有限公司 | 具有高透明度的柔性丙烯共聚物组合物 |
WO2006063905A1 (en) * | 2004-12-13 | 2006-06-22 | Basell Poliolefine Italia S.R.L. | Polyolefin composition, fibres and nonwoven fabrics |
WO2006082176A1 (en) * | 2005-02-03 | 2006-08-10 | Basell Polyolefine Gmbh | Process for producing thermoformed articles |
US20090305069A1 (en) * | 2005-04-21 | 2009-12-10 | Basell Poliolefine Italia S.R.L. | Biaxially oriented propylene polymer films |
US7662888B2 (en) | 2005-04-29 | 2010-02-16 | Japan Polypropylene Corporation | Polypropylene based heat shrinkable film |
US8247495B2 (en) * | 2010-02-19 | 2012-08-21 | Exxonmobil Chemical Patents Inc. | Elastomeric polymer blends and processes for their production |
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US9243138B2 (en) | 2011-03-18 | 2016-01-26 | Ineos Manufacturing Belgium Nv | Propylene-ethylene random copolymer |
CN104619767B (zh) | 2012-09-19 | 2017-08-08 | 英尼奥斯欧洲股份公司 | 丙烯‑乙烯无规共聚物 |
WO2014160311A1 (en) * | 2013-03-14 | 2014-10-02 | Braskem America, Inc. | Polypropylene impact copolymers with low haze |
US9115279B2 (en) | 2013-03-15 | 2015-08-25 | Asahi Kasei Plastics North America, Inc. | Polypropylene compounds with high impact performance and improved stress whitening resistance |
AU2014243188B2 (en) | 2013-03-26 | 2016-05-12 | Borealis Ag | Propylene copolymer with high impact properties |
EP2999722B1 (en) | 2013-05-22 | 2018-09-05 | Borealis AG | Polypropylene for film applications |
RU2534900C1 (ru) * | 2013-06-25 | 2014-12-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Казанский национальный исследовательский технологический университет" (ФГБОУ ВПО "КНИТУ") | Полимерная композиция, стойкая к воздействию ионизирующего излучения |
EP3019537B1 (en) | 2013-07-09 | 2022-12-21 | TotalEnergies OneTech Belgium | Propylene copolymer for bopp heat seal film layers. |
PT3064548T (pt) * | 2015-03-02 | 2017-07-11 | Borealis Ag | Composição de polipropileno combinando uma baixa temperatura de início de vedação, baixa turbidez, baixo teor de solúveis em hexano, e resistência ao rasgamento e temperatura de fusão melhoradas |
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- 2003-06-10 JP JP2004513350A patent/JP4423192B2/ja not_active Expired - Lifetime
- 2003-06-10 CA CA002483204A patent/CA2483204A1/en not_active Abandoned
- 2003-06-10 EP EP03759924.8A patent/EP1511783B1/en not_active Expired - Lifetime
- 2003-06-10 WO PCT/EP2003/006042 patent/WO2003106523A1/en active Application Filing
- 2003-06-10 CN CN03813458.6A patent/CN1290885C/zh not_active Expired - Lifetime
- 2003-06-10 US US10/517,588 patent/US7732530B2/en not_active Expired - Lifetime
- 2003-06-10 AU AU2003242656A patent/AU2003242656B2/en not_active Ceased
- 2003-06-10 RU RU2005100044/04A patent/RU2337115C2/ru not_active IP Right Cessation
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006316267A (ja) * | 2005-05-10 | 2006-11-24 | Sk Corp | 優れた耐衝撃性、曲げ弾性率および透明性を有するポリプロピレン組成物と該組成物から製造された製品 |
JP2009185259A (ja) * | 2008-02-08 | 2009-08-20 | Japan Polypropylene Corp | プロピレン/エチレン−αオレフィン系ブロック共重合体の製造方法 |
Also Published As
Publication number | Publication date |
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US7732530B2 (en) | 2010-06-08 |
EP1511783B1 (en) | 2013-07-31 |
RU2005100044A (ru) | 2005-06-10 |
AU2003242656A1 (en) | 2003-12-31 |
WO2003106523A1 (en) | 2003-12-24 |
EP1511783A1 (en) | 2005-03-09 |
CN1659200A (zh) | 2005-08-24 |
AU2003242656B2 (en) | 2008-04-03 |
BR0311862A (pt) | 2005-03-15 |
CA2483204A1 (en) | 2003-12-24 |
CN1290885C (zh) | 2006-12-20 |
US20060058463A1 (en) | 2006-03-16 |
AR040186A1 (es) | 2005-03-16 |
JP4423192B2 (ja) | 2010-03-03 |
RU2337115C2 (ru) | 2008-10-27 |
BR0311862B1 (pt) | 2013-08-06 |
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