WO2005090467A1 - Flexible propylene copolymer compositions having a high transparency - Google Patents
Flexible propylene copolymer compositions having a high transparency Download PDFInfo
- Publication number
- WO2005090467A1 WO2005090467A1 PCT/EP2005/003045 EP2005003045W WO2005090467A1 WO 2005090467 A1 WO2005090467 A1 WO 2005090467A1 EP 2005003045 W EP2005003045 W EP 2005003045W WO 2005090467 A1 WO2005090467 A1 WO 2005090467A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- propylene copolymer
- propylene
- weight
- film
- alkyl
- Prior art date
Links
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229920001577 copolymer Polymers 0.000 title claims abstract description 168
- 239000000203 mixture Substances 0.000 title claims abstract description 115
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 29
- 239000004711 α-olefin Substances 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 32
- 230000000737 periodic effect Effects 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- 125000005842 heteroatom Chemical group 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 16
- 239000008096 xylene Substances 0.000 claims description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 239000008395 clarifying agent Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 239000012632 extractable Substances 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052719 titanium Chemical group 0.000 claims description 4
- 239000010936 titanium Chemical group 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003906 silylidene group Chemical group [H][Si]([H])=* 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- -1 aluminum tert-butylbenzoate Chemical compound 0.000 description 49
- 238000012360 testing method Methods 0.000 description 40
- 230000000052 comparative effect Effects 0.000 description 28
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- 229920000642 polymer Polymers 0.000 description 23
- 239000000523 sample Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000002087 whitening effect Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 9
- 150000008040 ionic compounds Chemical class 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 7
- 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 7
- 239000000654 additive Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001990 intravenous administration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000725 suspension Substances 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
- 229910052796 boron Inorganic materials 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 6
- 239000002195 soluble material Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002877 alkyl aryl group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 239000007789 gas Substances 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
- 239000000155 melt Substances 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 229920005606 polypropylene copolymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 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 3
- 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
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
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- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 3
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- 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 2
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- WUJMJPSSISDRMH-CZYKHXBRSA-N C(C)[C@@](C(O)=CC1=CC=CC=C1)(O)[C@@H](O)[C@H](O)[C@H](O)C(O)=CC1=CC=CC=C1 Chemical compound C(C)[C@@](C(O)=CC1=CC=CC=C1)(O)[C@@H](O)[C@H](O)[C@H](O)C(O)=CC1=CC=CC=C1 WUJMJPSSISDRMH-CZYKHXBRSA-N 0.000 description 2
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- 238000003917 TEM image Methods 0.000 description 2
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical class [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 description 2
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- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
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- 241000408710 Hansa Species 0.000 description 1
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- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UYTHWPGWVQZOTA-UHFFFAOYSA-L [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC(=CC=3)C(C)(C)C)=C2C1[Zr+2]([SiH](C)C)C1C(C(C)C)=CC2=C1C=CC=C2C1=CC=C(C(C)(C)C)C=C1 Chemical compound [Cl-].[Cl-].CC1=CC(C(=CC=C2)C=3C=CC(=CC=3)C(C)(C)C)=C2C1[Zr+2]([SiH](C)C)C1C(C(C)C)=CC2=C1C=CC=C2C1=CC=C(C(C)(C)C)C=C1 UYTHWPGWVQZOTA-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- OFHCOWSQAMBJIW-AVJTYSNKSA-N alfacalcidol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)C[C@H](O)C1=C OFHCOWSQAMBJIW-AVJTYSNKSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MQXCDPDLPMAEIE-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)borinic acid Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1B(O)C1=C(F)C(F)=C(F)C(F)=C1F MQXCDPDLPMAEIE-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical compound [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 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
- 230000001419 dependent 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 compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 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
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 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
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 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
- 239000010410 layer Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 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
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 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
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229940054334 silver cation Drugs 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical class [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000001424 substituent group 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
- 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
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-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
- 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 1
- 239000003643 water by type Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
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
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
Definitions
- the invention relates to propylene copolymer compositions, to a process for producing the propylene copolymer compositions, to the use of the propylene copolymer compositions of the present invention for producing fibers, films or moldings and also to fibers, films or moldings comprising the propylene copolymer compositions of the present invention.
- Polymers of propylene can be processed to form shaped bodies which have advantageous mechanical properties, especially a high hardness, stiffness and shape stability. Consumer articles made of propylene polymers are used in a wide range of applications, e.g. as plastic containers, as household or office articles, toys or laboratory requisites.
- multiphase propylene copolymers having a good impact toughness and a decreasing stiffness can be prepared by means of Ziegler-Natta catalyst systems in a multistage polymerization reaction.
- the incorporation of ethylene-propylene copolymers having a high proportion of ethylene into a polymer matrix makes the multiphase propylene copolymer turbid. Poor miscibility of the flexible phase with the polymer matrix leads to a separation of the phases and thus to turbidity and to poor transparency values of the heterogeneous copolymer.
- the ethylene-propylene rubber prepared by means of conventional Ziegler-Natta catalysts also has a very inhomogeneous composition. It is also known that multiphase copolymers of propylene can be prepared using metallocene catalyst systems.
- WO 94/28042 and EP-A 1 002 814 disclose multiphase copolymers of propylene. However, no propylene copolymer compositions having a propylene copolymer matrix are described.
- WO 01/48034 relates to metallocene compounds by means of which propylene copolymers having a high molar mass and a high copolymerized ethylene content can be obtained under industrially relevant polymerization conditions.
- Multiphase propylene copolymers having a high stiffness/impact toughness level are obtainable in this way.
- no flexible propylene copolymer compositions having a high transparency are described.
- WO 03/106523 relates to a flexible propylene composition obtained by a multistage process.
- this document does not describes the particular balance of properties of the composition of the present invention, due to the particular values of comonomer content of said composition, in particular this document does not describes an ethylene content lower than 1% in the propylene copolymer A).
- propylene polymer films can be produced from random copolymer or heterophasic polymer compositions. However, the properties of these films limit their usefulness across a broad range of film applications requiring diverse properties.
- the present invention relates to a propylene copolymer composition
- a propylene copolymer composition comprising: A) from 50% to 80% by weight of a propylene copolymer containing from 0.05 to 0.99% by weight of an alpha olefins having from 2 to 10 carbon atoms other than propylene; and B) from 20% to 50%) by weight of one propylene copolymer containing from about 7.01% to about 20.0%, preferably about 7.01% to about 9.99%, more preferably about 8.0% to about 9.6% by weight of an alpha olefins having from 2 to 10 carbon atoms other than propylene; said propylene copolymer composition having the following characteristics: (i) MFR (230°C/2, 16 kg) comprised between 1 and 20 g/10 min; (ii) tensile E modulus comprised between 400 and 800 MPa.
- the present invention relates to a film produced from a propylene copolymer composition
- a propylene copolymer composition comprising A) from about 50% to about 80% by weight of a propylene copolymer containing from about 0.05 to about 0.99% by weight of alpha olefins having from 2 to 10 carbon atoms other than propylene; and B) from about 20%> to about 50% by weight of a propylene copolymer containing from about 7.01% to about 9.99% by weight of alpha olefins having from 2 to 10 carbon atoms other than propylene; wherein components A) and B) are obtained using a catalyst system based on metallocene compounds, and the propylene copolymer composition has an MFR of from about 1 to about 20 and a tensile E modulus of about 400 to about 800 MPa; and wherein the film has a haze less than about 10.0% and a dart impact greater than about 150 gms for a 1 mil thickness of film.
- the propylene polymer composition of the invention comprises: A) from 50% to 80% by weight of a propylene copolymer containing from about 0.05 to about 0.99% by weight of an alpha olefin having from 2 to 10 carbon atoms other than propylene; and B) from 20% to 50%) by weight of a propylene copolymer containing from about 7.01%) to about 20.0%, preferably about 7.01 to 9.99 % by weight, more preferably about 8.0%) to about 9.6% by weight of alpha olefin having from 2 to 10 carbon atoms other than propylene; said propylene copolymer composition having the following characteristics: (i) MFR (230°C/2.16 kg) comprised between 1 and 20 g/lOmin, preferably between 6 and 12 g/lOmin
- the propylene copolymer composition has the melting point, measured as described below, comprised between 143°C and 150°C; more preferably comprised between 145°C and 150°C.
- the propylene copolymer composition has haze measured according to ASTM D 1003 comprised between 25% and 40%; preferably between 25% and 35%; more preferably between 31%> and 35%, wherein the haze is measured on the product as such without the adding of clarifying agents.
- the propylene copolymer composition of the present invention is preferably obtainable by means of a two-stage or multistage polymerization using a catalyst system based on metallocene compounds.
- the propylene copolymer A usually forms a three-dimensionally coherent phase in which the phase of the propylene copolymer B is embedded. Such a coherent phase in which one or more other phases are dispersed is frequently referred to as the matrix.
- the matrix usually also makes up the major proportion by weight of the polymer composition.
- the propylene copolymer B is generally dispersed in finely divided form in the matrix. Furthermore, the diameter of the then isolated domains of the propylene copolymer B is usually from 100 nm to 1000 nm.
- the determination of the geometry of the individual phases of the propylene copolymer compositions can be carried out, for example, by evaluation of contrasted transmission electron micrographs (TEMs).
- TEMs contrasted transmission electron micrographs
- Prefened alpha-olefins are linear C -C ⁇ 0 -l- alkenes.
- olefins are ethylene and linear C 4 -C ⁇ )-l-alkenes such as 1— butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-decene, in particular ethylene and/or 1 -butene.
- the propylene copolymer A present in the propylene copolymer compositions of the present invention is a propylene copolymer containing from 0.05 to 0.99% by weight of alpha-olefins other than propylene.
- Preferred propylene copolymers contain from 0.5 to 0.90% by weight, in particular from 0.5 to 0.8% by weight, of alpha-olefins other than propylene.
- comonomers preference is given to using ethylene or linear C 4 -C 1 0- 1- alkenes or mixtures thereof, in particular ethylene and/or 1 -butene.
- the component B present in the propylene copolymer compositions of the present invention is made up of at least one propylene copolymer containing; from about 7.01% to about 20.0%, preferably, 7.01% to 9.99%, more preferably, 8.0% to about 9.6% by weight of alpha-olefins other than propylene.
- Preferred comonomers are ethylene or linear C 4 - C ⁇ o-1-alkenes or mixtures thereof, in particular ethylene and/or 1-butene.
- monomers containing at least two double bonds e.g. 1 ,7-octadiene or 1,9-decadiene, are additionally used.
- the composition of the present invention contains from 50% to 80%> by weight of the copolymer A; preferably from 60%) to 75% by weight; more preferably from 65% to 72% by weight.
- the composition object of the present invention contains from 20% to 50% by weight of the propylene copolymer B; preferably from 25 ⁇ to 40% by weight; more preferably from 28% to 35%) by weight.
- the proportion of n-hexane-soluble material in the propylene copolymer compositions of the present invention is preferably ⁇ 2.6%> by weight, particularly preferably ⁇ 2.0 by weight and in particular ⁇ 1.0% by weight.
- the determination of the proportion of n-hexane-soluble material is canied out by a modified FDA method by extraction of about 2.5 g of material with one liter of n- hexane at 50°C. According to the FDA method, an extruded film is used as sample.
- the same values for the proportion of n-hexane-soluble material are obtained using samples composed of granulated material or a granulated material which has been milled to a mean particle diameter of, for example, 100 ⁇ m.
- the propylene copolymer compositions of the present invention preferably have a haze value comprised between 25%) and 40%, preferably between 25% and 35%; more preferably between 31%) and 35%, based on a film thickness of the propylene copolymer composition of 1 mm, measured without the aid of clarifying agents according to ASTM D 1003.
- the haze value is a measure of the turbidity of the material and is thus a parameter which characterizes the transparency of the propylene copolymer compositions.
- the haze value is also dependent on the film thickness. The thinner the layer, the lower the haze value.
- a 1 mil (25.4 ⁇ m) thickness of film produced with the compositions of the invention preferably has a haze value of less than about 10%, more preferably less than about 5%, and most preferably less than about 2% » measured without the aid of clarifying agents.
- clarifying agents known in the art such as sodium benzoate, aluminum tert-butylbenzoate, dibenzylidenesorbitol or its C ⁇ -C 8 -alkyl-substituted derivatives such as methyldibenzylidenesorbitol, 3 ,4-dimethylbenzylidensorbitol, ethyldibenzylidenesorbitol or dimethyldibenzylidenesorbitol or salts of diesters of phosphoric acid, e.g.
- propylene copolymer compositions of the present invention have a tensile E modulus determined in a tensile test in accordance with ISO 527-2:1993 in the range from 400 to 800 MPa, preferably from 550 MPa to 750 MPa and in particular in the range from 600 MPa to 700 MPa.
- Propylene polymers are tough materials at room temperature, i.e. plastic deformation occurs under mechanical stress only before the material breaks. However, at reduced temperatures, propylene polymers display brittle fracture, i.e. fracture occurs virtually without deformation or at a high propagation rate.
- a parameter which describes the temperature at which the deformation behavior changes from tough to brittle is the "brittle/tough transition temperature".
- the propylene copolymer A is generally present as matrix and the propylene copolymer B, which usually has a stiffness lower than that of the matrix and acts as impact modifier, is dispersed therein in finely divided form.
- Such an impact modifier not only increases the toughness at elevated temperatures but also reduces the brittle/tough transition temperature.
- the brittle/tough transition temperature is determined by means of puncture tests in accordance with ISO 6603-2, in which the temperature is reduced in continuous steps.
- the force/displacement graphs recorded in the puncture tests enable conclusions as to the deformation behavior of the test specimens at the respective temperature to be drawn and thus allow the brittle/tough transition temperature to be determined.
- the temperature is reduced in steps of 2°C and the brittle/tough transition temperature is defined as the temperature at which the total deformation is at least 25% below the mean total deformation of the preceding 5 measurements; here, the total deformation is the displacement through which the punch has traveled when the force has passed through a maximum and dropped to 3%> of this maximum force.
- the total deformation at 23 °C is employed as reference value and the brittle/tough transition temperature is the temperature at which the total deformation is at least 25% below the total deformation at 23°C.
- Prefened propylene copolymer compositions of the present invention have a brittle/tough transition temperature comprised between -20°C and 0°C, preferably comprised between -15°C and -3 °C and more preferably comprised between -10°C and -5°C.
- the propylene copolymer compositions of the present invention usually display good stress whitening behavior.
- stress whitening is the occunence of whitish discoloration in the stressed region when the polymer is subjected to mechanical stress.
- white discoloration is caused by small voids being formed in the polymer under mechanical stress.
- Good stress whitening behavior means that no or only very few regions having a whitish discoloration occur under mechanical stress.
- One method of quantifying stress whitening behavior is to subject defined test specimens to a defined impact stress and then to measure the size of the resulting white spots. Accordingly, in the dome method, a falling dart is dropped onto a test specimen in a falling dart apparatus in accordance with DIN 53443 Part 1.
- a falling dart having a mass of 250 g and a punch of 5 mm in diameter is used.
- the dome radius is 25 mm and the drop is 50 cm.
- the test specimens used are injection-molded circular disks having a diameter of 60 mm and a thickness of 2 mm, and each test specimen is subjected to only one impact test.
- the stress whitening is reported as the diameter of the visible stress whitening region in mm; the value reported is in each case the mean of 5 test specimens and the individual values are determined as the mean of the two values in the flow direction on injection molding and perpendicular thereto on the side of the circular disk opposite that on which impact occurs.
- the propylene copolymer compositions of the present invention generally display no or only very little stress whitening determined by the dome method at 23°C.
- Very particularly prefened propylene copolymer compositions display no stress whitening at all in the test canied out by the dome method at 23°C.
- the propylene copolymer compositions of the present invention generally further comprise customary amounts of customary additives known to those skilled in the art, e.g.
- Customary stabilizers include antioxidants such as sterically hindered phenols, sterically hindered amines or UV stabilizers, processing stabilizers such as phosphites or phosphonites, acid scavengers such as calcium stearate or zinc stearate or dihydrotalcite, as well as calcium, zinc and sodium caprylate salts.
- the propylene copolymer compositions of the present invention contain one or more stabilizers in amounts of up to 2% by weight.
- Suitable lubricants and mold release agents are, for example, fatty acids, calcium, sodium or zinc salts of fatty acids, fatty acid amides or low molecular weight polyolefin waxes, which are usually used in concentrations of up to 2% by weight.
- Possible fillers are, for example, talc, calcium carbonate, chalk or glass fibers, and these are usually used in amounts of up to 50% by weight.
- suitable nucleating agents are inorganic additives such as talc, silica or kaolin, salts of monocarboxyhc or polycarboxylic acids, e.g.
- the nucleating agent content of the propylene copolymer composition is generally up to 5% by weight.
- the propylene copolymer compositions of the present invention contain from 0.1 to 1% by weight, preferably from 0.15 to 0.25% by weight, of a nucleating agent, in particular dibenzylidenesorbitol or a dibenzylidenesorbitol derivative, particularly preferably dimethyldibenzylidenesorbitol.
- a nucleating agent in particular dibenzylidenesorbitol or a dibenzylidenesorbitol derivative, particularly preferably dimethyldibenzylidenesorbitol.
- the structure of the propylene-ethylene copolymers B can be determined by means of 13 C-NMR spectroscopy as well as by means IR spectroscopy. Evaluation of the spectrum is prior art and can be canied out by a person skilled in the art using, for example, the method described by H. N. Cheng, Macromolecules 17 (1984), pp. 1950-1955 or L. Abis et al., Makromol. Chemie 187 (1986), pp. 1877-1886.
- propylene copolymer compositions obtained from propylene and ethylene have a PEP/PE ⁇ ratio in the range from 0.9 to 2.2, preferably in the range from 1 to 2.0, particularly preferably in the range from 1.3-2.0.
- the properties of the propylene copolymer compositions of the present invention are also determined by the viscosity ratio of the propylene copolymer B and the propylene copolymer A, i.e.
- the propylene copolymer compositions can be fractionated by means of TREF fractionation (Temperature Rising Elution Fractionation).
- the propylene copolymer B is then the combined fractions which are eluted by xylene at temperatures up to and including 70°C.
- the propylene copolymer A is obtained from the combined fractions which are eluted by xylene at temperatures above 70°C.
- a clean TREF fractionation presents difficulties since the elution temperature of the propylene copolymer A drops below 70°C with increasing comonomer content.
- One way of obtaining information about the individual components is to cany out the examination of the propylene copolymer A using the polymer taken from the reactor directly after the first polymerization step.
- the propylene copolymer B can be separated from the product of a separate test run in which a polymerization identical to that for the propylene copolymer composition to be examined has been canied out but with no addition of comonomer in the first polymerization step, i.e. a propylene homopolymer has been prepared.
- the ratio of the shear viscosity of propylene copolymer B to that of propylene copolymer A at a shear rate of 100s "1 is in the range from 0.3 to 2.5, preferably from 0.5 to 2 and particularly preferably in the range from 0.7 to 1.75.
- the propylene copolymer compositions of the present invention preferably have a nanow molar mass distribution M w /M n .
- the molar mass distribution M w /M n is, for the purposes of the invention, the ratio of the weight average molar mass M w to the number average molar mass M n .
- the molar mass distribution M w /Mschreib is preferably in the range from 1.5 to 3.5, particularly preferably in the range from 2 to 2.5 and in particular in the range from 2 to 2.4.
- the molar mass M n of the propylene copolymer compositions of the present invention is preferably in the range from 20,000 g/mol to 500,000 g/mol, particularly preferably in the range from 50,000 g/mol to 200,000 g/mol and very particularly preferably in the range from 80,000 g/mol to 150,000 g/mol.
- the composition of the present invention is preferably canied out in a multistage polymerization process comprising at least two successive polymerization steps which are generally canied out in a reactor cascade.
- the polymerization can be canied out in a known manner in bulk, in suspension, in the gas phase or in a supercritical medium. It can be carried out batchwise or preferably continuously. Solution processes, suspension processes, stined gas-phase processes or gas-phase fluidized-bed processes are possible. As solvents or suspension media, it is possible to use inert hydrocarbons, for example isobutane, or else the monomers themselves. It is also possible to carry out one or more steps of the process of the present invention in two or more reactors. The size of the reactors is not of critical importance for the process of the present invention. It depends on the output which is to be achieved in the individual reaction zone(s).
- the preceding polymerization of the propylene copolymers A can be canied out either in bulk, i.e. in liquid propylene as suspension medium, or else from the gas phase. If all polymerizations take place from the gas phase, they are preferably canied out in a cascade comprising stined gas-phase reactors which are connected in series and in which the pulverulent reaction bed is kept in motion by means of a vertical stiner.
- the reaction bed generally consists of the polymer which is polymerized in the respective reactor.
- the initial polymerization of the propylene copolymers A is canied out in bulk, preference is given to using a cascade made up of one or more loop reactors and one or more gas-phase fluidized-bed reactors. The preparation can also be carried out in a multizone reactor.
- To prepare the propylene copolymers present in the propylene copolymer compositions of the present invention preference is given to using catalyst systems based on metallocene compounds of transition metals of group 3, 4, 5 or 6 of the Periodic Table of the Elements. Particular preference is given to catalyst systems based on metallocene compounds of the formula (I),
- M is zirconium, hafnium or titanium, preferably zirconium
- X are identical or different and are each, independently of one another, hydrogen or halogen or an -R, -OR, -OSO 2 CF 3 , -OCOR, -SR, -NR 2 or -PR 2 group, where R is linear or branched d-C ⁇ -alkyl, C 3 -C 2 o-cycloalkyl which may be substituted by one or more C ⁇ -C ⁇ o-alkyl radicals, C 6 -C 2 o-aryl, C -C 2 o-alkylaryl or C 7 -C 2 o-arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, preferably C ⁇ -C ⁇ o-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl
- L is a divalent bridging group selected from the group consisting of C ⁇ -C o-alkylidene radicals, C 3 -C 2 o-cycloalkylidene radicals, C 6 -C 2 o-arylidene radicals, C 7 -C o- alkylarylidene radicals and C -C 2 o-arylalkylidene radicals, which may contain heteroatoms of groups 13-17 of the Periodic Table of the Elements, or a silylidene group having up to 5 silicon atoms, e.g.
- L preferably is a radical selected from the group consisting of -SiMe - - SiPh 2 - -SiPhMe-, -SiMe(SiMe 3 )-, -CH 2 - -(CH 2 ) 2 - -(CH 2 ) 3 - and -C(CH 3 ) 2 -
- R 1 is linear or branched C ⁇ -C 2 ⁇ -alkyl, C 3 -C 2u -cycloalkyl which may be substituted by one or more Ci-Cio-alkyl radicals, C 6 -C 2 o-aryl, C 7 -C 2 o-alkylaryl or C 7 -C 2 o-arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, where R 1 is preferably unbranched in the ⁇ position and is preferably a linear or branched Ci-Cio-alkyl group which is unbranched in the ⁇ position, in particular a linear C ⁇ -C 4 -alkyl group such as methyl, ethyl, n-propyl or n-butyl,
- R 2 is a group of the formula -C(R 3 ) 2 R 4 , where R are identical or different and are each, independently of one another, linear or branched C ⁇ -C 20 -alkyl, C 3 -C 2 ⁇ -cycloalkyl which may be substituted by one or more Ci-Cio-alkyl radicals, C 6 -C 2 o-aryl, C -C 2 o-alkylaryl or C 7 -C 2 o-arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, or two radicals R 3 may be joined to form a saturated or unsaturated C 3 -C 2 o-ring, where R 3 is preferably a linear or branched C ⁇ -C ⁇ o-alkyl group, and
- R 4 is hydrogen or linear or branched C ⁇ -C 2 o-alkyl, C 3 -C 2 o-cycloalkyl which may be substituted by one or more Ci-Cio-alkyl radicals, C 6 -C 2 o-aryl, C 7 -C 2 o-alkylaryl or C 7 -C 2 o-arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, where R 4 is preferably hydrogen,
- T and T' are divalent groups of the formulae (II), (III), (IV), (V) or (VI),
- R 5 are identical or different and are each, independently of one another, hydrogen or halogen or linear or branched C ⁇ -C 2 o-alkyl, C 3 -C 2 o-cycloalkyl which may be substituted by one or more Ci- o-alkyl radicals, C 6 -C 2 o-aryl, C 7 -C 2 ⁇ -alkylaryl or C 7 -C 2 o-arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, where R 5 is preferably hydrogen or a linear or branched C ⁇ -C ⁇ o-alkyl group, in particular a linear C ⁇ -C 4 -alkyl group such as methyl, ethyl, n-propyl or n-butyl, and R 6 are identical or different and are each, independently of one another, halogen or linear or branched C 1 -C o-alkyl, C 3 -C 2
- R 7 are identical or different and are each, independently of one another, hydrogen or halogen or linear or branched C ⁇ -C 2u -alkyl, C 3 -C 2 o-cycloalkyl which may be substituted by one or more Ci-Cio-alkyl radicals, C 6 -C 2 o-aryl, C 7 -C o-alkylaryl or C 7 -C 2 o -arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, or two radicals R 7 may be joined to form a saturated or unsaturated C 3 -C 2 o ring, where R 7 is preferably a hydrogen atom, and
- R 8 is hydrogen or halogen or linear or branched C ⁇ -C o-alkyl, C -C 2 o-cycloalkyl which may be substituted by one or more Ci-Cio-alkyl radicals, C 6 -C 2 ⁇ -aryl, C 7 - C 2 o-alkylaryl or C 7 -C 2 o-arylalkyl and may contain one or more heteroatoms of groups 13-17 of the Periodic Table of the Elements or one or more unsaturated bonds, where R 8 is preferably a branched alkyl group of the formula -C(R 9 ) 3 , where
- R 9 are identical or different and are each, independently of one another, a linear or branched C ⁇ -C 6 -alkyl group or two or three of the radicals R 9 are joined to form one or more ring systems. It is prefened that at least one of the groups T and T' is substituted by a radical R 6 of the formula (VII); it is particularly prefened that both groups are substituted by such a radical. Very particular preference is given to at least one of the groups T and T' being a group of the formula (IV) which is substituted by a radical R 6 of the formula (VII) and the other either has the formula (II) or (IV) and is likewise substituted by a radical R 6 of the formula (VII). The greatest preference is given to catalyst systems based on metallocene compounds of the formula (VIII),
- metallocene compounds and methods of preparing them are described, for example, in WO 01/48034 and the European patent application No. 01204624.9. It is also possible to use mixtures of various metallocene compounds or mixtures of various catalyst systems. However, preference is given to using only one catalyst system comprising one metallocene compound, which is used for the polymerization of the propylene copolymer A and the propylene copolymer B.
- Examples of useful metallocene compounds are dimethylsilanediyl(2-ethyl-4-(4'-tert-butylphenyl)indenyl)(2-isopropyl-4-(4'-tert- butylphenyl)indenyl)zirconium dichloride, dimethylsilanediyl(2-methyl-4-(4'-tert-butylphenyl)indenyl)(2-isopropyl-4-(l- naphthyl)indenyl)zirconium dichloride, dimethylsilanediyl(2-methyl-4-phenyl- 1 -indenyl)(2-isopropyl-4-(4 '-tert-butylphenyl)- 1 - indenyl)zirconium dichloride, dimethylsilanediyl(2-methylthiapentenyl)(2-isopropyl-4-(4'-tert- butylphenyl)
- the prefened catalyst systems based on metallocene compounds generally further comprise cation-forming compounds as cocatalysts.
- Suitable cation-forming compounds which are able to react with the metallocene compound to convert it into a cationic compound are, for example, compounds such as an aluminoxane, a strong uncharged Lewis acid, an ionic compound having a Lewis-acid cation or an ionic compound containing a Bronsted acid as cation.
- the cation-forming compounds are frequently also refened to as compounds which form metallocenium ions.
- aluminoxanes it is possible to use, for example, the compounds described in WO 00/31090. Particularly useful compounds are open-chain or cyclic aluminoxane compounds of the formula (IX) or (X)
- R 21 is a C ⁇ -C 4 -alkyl group, preferably a methyl or ethyl group, and m is an integer from 5 to 30, preferably from 10 to 25.
- These oligomeric aluminoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water.
- the oligomeric aluminoxane compounds obtained in this way are generally in the form of mixtures of both linear and cyclic chain molecules of various lengths, so that m is to be regarded as a mean.
- the aluminoxane compounds can also be present in admixture with other metal alkyls, preferably aluminum alkyls.
- aluminoxane compounds of the formulae (IX) or (X) may be used in place of the aluminoxane compounds of the formulae (IX) or (X). It has been found to be advantageous to use the metallocene compounds and the aluminoxane compounds in such amounts that the atomic ratio of aluminum from the aluminoxane compounds to the transition metal from the metallocene compound is in the range from 10:1 to 1000:1, preferably from 20:1 to 500:1 and in particular in the range As strong, uncharged Lewis acids, preference is given to compounds of the formula
- Lewis acids are mentioned in WO 00/31090. Particular preference is given to compounds of the formula (XI) in which X 1 , X 2 and X are identical, preferably tris(pentaffuorophenyl)borane.
- Strong uncharged Lewis acids suitable as cation-forming compounds also include the reaction products from the reaction of a boronic acid with two equivalents of a trialkylaluminum or the reaction products from the reaction of a trialkylaluminum with two equivalents of an acidic fluorinated, in particular perfluorinated, carbon compound such as pentafluorophenol or bis(pentafluorophenyl) borinic acid.
- Suitable ionic compounds containing Lewis-acid cations include salt-like compounds of the cation of the formula (XII) [(Y a+ )Q ⁇ Q2...Q z ] d+ (xii) where
- Y is an element of groups 1 to 16 of the Periodic Table of the Elements
- Qi to Q z are singly negatively charged groups such as C ⁇ -C 28 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having from 6 to 20 carbon atoms in the aryl radical and from 1 to 28 carbon atoms in the alkyl radical, C 3 -C ⁇ o- cycloalkyl which may be substituted by Ci-Cio-alkyl groups, or halogen, Ci- C 28 -alkoxy, C 6 -Ci 5 -aryloxy, silyl or mercapto groups, a is an integer from 1 to 6 and z is an integer from 0 to 5, d is the difference a-z, but d is greater than or equal to 1.
- groups such as C ⁇ -C 28 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having
- Lewis-acid cations are carbonium cations, oxonium cations and sulfonium cations and also cationic transition metal complexes. Particular mention may be made of the triphenylmethyl cation, the silver cation and the l,l'-dimethylfenocenyl cation. They preferably have noncoordinating counterions, in particular boron compounds as are mentioned in WO 91/09882, preferably tetrakis(pentafluorophenyl)borate. Salts having noncoordinating anions can also be prepared by combining a boron or aluminum compound, e.g.
- an aluminum alkyl with a second compound which can react to link two or more boron or aluminum atoms, e.g. water, and a third compound which forms an ionizing ionic compound with the boron or aluminum compound, e.g. triphenylchloromethane.
- a fourth compound which likewise reacts with the boron or aluminum compound, e.g. pentafluorophenol, can additionally be added.
- Ionic compounds containing Br ⁇ nsted acids as cations preferably likewise have noncoordinating counterions. As Br ⁇ nsted acids, particular preference is given to protonated amine or aniline derivatives. Preferred cations are N,N-dimethylanilinium,
- Prefened ionic compounds C) are, in particular, N,N-dimethylanilmium tetrakis(pentafluorophenyl)borate, N,N-dimethylcyclohexylammonium tetrakis(pentafluorophenyl)borate and N,N-dimethylbenzylammonium tetrakis(pentafluorophenyl)borate.
- borate anions it is also possible for two or more borate anions to be joined to one another, as in the dianion [(C 6 F 5 ) 2 B-C 6 F 4 -B(C 6 F 5 ) 2 ] 2' , or the borate anion can be bound via a bridge having a suitable functional group to the support surface.
- suitable cation-forming compounds are listed in WO 00/31090.
- the amount of strong, uncharged Lewis acids, ionic compounds having Lewis-acid cations or ionic compounds containing Bronsted acids as cations is preferably from 0.1 to 20 equivalents, preferably from 1 to 10 equivalents, based on the metallocene compound.
- Suitable cation-forming compounds also include boron-aluminum compounds such as di[bis(pentafluorophenylboroxy)]methylalane. Such boron-aluminum compounds are disclosed, for example, in WO 99/06414. It is also possible to use mixtures of all of the abovementioned cation-forming compounds. Prefened mixtures comprise aluminoxanes, in particular methylaluminoxane, and an ionic compound, in particular one containing the tetrakis(pentafluorophenyl)borate anion, and/or a strong uncharged Lewis acid, in particular tris(pentafluorophenyl)borane.
- aluminoxanes in particular methylaluminoxane
- an ionic compound in particular one containing the tetrakis(pentafluorophenyl)borate anion, and/or a strong uncharged Lewis acid, in particular tris(pent
- the prefened catalyst systems based on metallocene compounds can further comprise, as additional component, a metal compound of the formula (XIII), M 3 (R 22 ) r (R 23 ) s (R 24 )t (XIII) where M 3 is an alkali metal, an alkaline earth metal or a metal of group 13 of the Periodic Table, i.e.
- R 22 is hydrogen, Ci-Cio-alkyl, C 6 -C ⁇ 5 -aryl, alkylaryl or arylalkyl each having from 1 to 10 carbon atoms in the alkyl part and from 6 to 20 carbon atoms in the aryl part
- R and R are each hydrogen, halogen, Ci-Cio-alkyl, C 6 -Ci 5 -aryl, alkylaryl, arylalkyl or alkoxy each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical
- r is an integer from 1 to 3 and s and t are integers from 0 to 2, where the sum r+s+t conesponds to the valence of M 3
- the metal compound of the formula (XIII) is not identical to the cation-forming compound. It is also possible to use mixtures of various metal compounds of the formula (XIII).
- M 3 is lithium, magnesium or aluminum and
- R 23 and R 24 are each d-Cio-alkyl.
- Particularly prefened metal compounds of the formula (XIII) are n-butyllithium, n- butyl-n-octylmagnesium, n-butyl-n-heptylmagnesium, tri-n-hexylaluminum, triisobutylaluminum, triethyl-aluminum and trimethylaluminum and mixtures thereof. If a metal compound of the formula (XIII) is used, it is preferably used in such an amount that the molar ratio of M 3 from formula (XIII) to the transition metal from the metallocene compound is from 800:1 to 1:1, in particular from 200: 1 to 2:1.
- Suitable supports are, for example, porous organic or inorganic inert solids such as finely divided polymer powders, talc, sheet silicates or inorganic oxides.
- Inorganic oxides suitable as supports may be found among the oxides of elements of groups 2, 3, 4, 5, 13, 14, 15 and 16 of the Periodic Table of the Elements. Preference is given to oxides or mixed oxides of the elements calcium, aluminum, silicon, magnesium or titanium and also conesponding oxide mixtures.
- Other inorganic oxides which can be used alone or in combination with the abovementioned oxidic supports are, for example, ZrO or B 2 O 3 .
- Prefened oxides are silicon dioxide and aluminum oxide, in particular silica gels or pyrogenic silicas.
- An example of a prefened mixed oxide is calcined hydrotalcite.
- the support materials used preferably have a specific surface area in the range from 10 to 1000 m 2 /g, preferably from 50 to 500 m 2 /g and in particular from 200 to 400 m 2 /g, and a pore volume in the range from 0.1 to 5 ml/g, preferably from 0.5 to 3.5 ml/g and in particular from 0.8 to 3.0 ml/g.
- the mean particle size of the finely divided supports is generally in the range from 1 to 500 ⁇ m, preferably from 5 to 350 ⁇ m and in particular from 10 to 100 ⁇ m.
- propylene copolymers present in the propylene copolymer compositions of the present invention preference is given to firstly forming the propylene copolymer A in a first step by polymerizing from 80% by weight to 99% by weight, based on the total weight of the mixture, of propylene in the presence of further olefins, usually from 40°C to 120°C and pressures in tkte range from 0.5 bar to 200 bar.
- the polymer obtainable by means of this reaction siibsequently has a mixture of from 2 to 95% by weight of propylene and from 5% to 98° o by weight of further olefins polymerized onto it in a second step, usually at from 40°C to 120°C and pressures in the range from 0.5 bar to 200 bar.
- the polymerization of the propylene copolymer A is preferably canied out at from 60 to 80°C, particularly preferably from 65 to 75 °C, and a pressure from 5 to 10O bar, particularly preferably from 10 bar to 50 bar.
- the polymerization of the propylene copolymer B is preferably canied out at -from 60 to 80°C, particularly preferably from 65 to 75 °C, and a pressure of from 5 to 100 b>ar, particularly preferably from 10 bar to 50 bar.
- molar mass regulators such as hydrogen or inert gases such as nitrogen or argon.
- the amounts of the monomers added in the individual steps and also the process conditions such as pressure, temperature or the addition of molar mass regulators such as hydrogen is chosen so that the polymers formed have the desired properties.
- the scope of the invention includes the technical teaxhing that a propylene copolymer composition which has a low stiffness and at the same time a good transparency is obtainable, for example, by setting defined comonomer contents of the propylene copolymers A and B and the viscosity ratio of propylene copolymer A to propylene copolymer B.
- the composition of the propylene copolymer B has significant effects on the transparency of the propylene copolymer compositions of the present invention. A reduction in the comonomer content of the propylene copolymer B leads to an improved transparency, while at the same time the stiffness of the matrix also decreases as a result of the better compatibility with the propylene copolymer B.
- the propylene copolymer B or constituents of the propylene copolymer B, thus act as plasticizer(s) for the matrix.
- An increase in the comonomer content of the propylene copolymer B results in an improvement in the impact toughness, particularly at low temperatures, but at the expense of the transparency.
- the proportion of propylene copolymer B which is miscible with the matrix and acts as plasticizer is decreased, as a result of which, the stiffness of the copolymer increases.
- the transparency of the propylene copolymer compositions of the present invention is virtually independent of the proportion of the propylene copolymer B present therein. Adjustment of the viscosity ratio of propylene copolymer A to propylene copolymer B influences the dispersion of the propylene copolymer B in the polymer matrix and thus has effects on the transparency of the propylene copolymer compositions and on the mechanical properties.
- the propylene copolymer compositions of the present invention display a high flexibility in combination with a good transparency. Furthermore, they have low proportions of n-hexane-soluble material, good stress whitening behavior and also a good impact toughness at low temperatures, a high stiffness and good heat distortion resistance.
- the propylene copolymer compositions of the present invention can also be used in a temperature range which places high demands on the material properties of the copolymers at temperatures below freezing point.
- a further advantage is that the shrinkage behavior of the propylene copolymer compositions conesponds to that of propylene polymers. In the case of moldings consisting of different materials, for example containers which have been produced from one propylene polymer and are to be closed with a flexible lid, this leads to advantages in respect of accuracy of fit and freedom from leaks, in particular when the containers are subjected to washing at elevated temperatures.
- the copolymers of the present invention are suitable for producing fibers, films or moldings, in particular for producing injection-molded parts, films, sheets or large hollow bodies, e.g. by means of injection-molding or extrusion processes.
- Possible applications are the fields of packaging, household articles, containers for storage and transport, office articles, electrical equipment, toys, laboratory requisites, motor vehicle components and gardening requisites, in each case especially for applications at low temperatures.
- the copolymers of the invention are used to produce films, the films can be oriented or non-oriented films, and can be used alone or as part of a co-extruded multilayer structure.
- the films may also be used as a coating layer to coat a substrate or as part of a laminate structure with other polyolefin films.
- the films are cast films.
- the films possess properties that make them suitable for a wide variety of applications, such as in diapers, IV bags, stationary covers, sterilizable medical films and film packaging and cooking.
- the films have a dart impact value, measured according to ASTM D 1709 A, of greater than about 150 gm, more preferably greater than about 200 gm, most preferably greater than about 300 gm for a 1 mil (25.4 ⁇ m) thickness of film.
- the films have a puncture resistance of greater than about 300 J/cm3, more preferably 400 J/cm3, for a 1 mil (25.4 ⁇ m) thickness of film.
- puncture resistance is measured with an Instron Model 4202 testing apparatus commercially available from Instron Corporation using a 200 lb load cell.
- the test was conducted in a standard laboratory atmosphere of 23 °C +/- 2°C and 50 +/- 5 %> relative humidity, and the probe penetration was measured.
- the films of the invention also possess good food packaging characteristics.
- the films have a xylene solubles of less than about 30.0%), more preferably less than 25%, measured as described below.
- the films have a water vapor transmission rate ("WVTR"), measured according to ASTM F1249, of greater than about 11.6 gm/m2-day, preferably greater than about 14.0 gm/m2-day for a 1 mil (25.4 ⁇ m) thickness of film; an oxygen transmission rate (“OTR”), measured according to ASTM D3985, of preferably greater than about 3875 gm/m2-day, more preferably greater than 4650 gm/m2-day for a 1 mil (25.4 ⁇ m) thickness of film; and a carbon dioxide transmission rate (“CO2TR”), measured according to ASTM D3985, of preferably greater than about 19,375 cc/m2-day, more preferably greater than about 23,250 cc/m2-day for a 1 mil (25.4 ⁇ m) thickness of film.
- WVTR water
- the films have a heat resistance of at least 116°C, allowing them to be used in food packaging applications where the package is heated.
- heat resistance is measured by first stacking 10 plies of 10.2 cm x 10.2 cm of film. The stacked film sample is placed in a forced air oven and then exposed to a given temperature for 15 minutes until the desired temperature is reached. A light weight sample rack is placed over the sample just to keep it from moving. After 15 minutes of exposure, the sample is taken out of the oven and separated. If the film comes apart without sticking, it is termed as a "pass", if not it is a failure.
- the highest temperature at which the film samples come apart without sticking is determined as the "Heat Resistance.”
- the optical and film toughness characteristics of the films of the invention have been recited on the basis of a film thickness of about 1 mil (25.4 ⁇ m). However, one skilled in the art would recognize that the films of the invention can generally have any thickness that meet the optical property and film toughness characteristics required for the particular application. Generally, it is expected that the films of the invention will be from about 0.5 mil (12.7 ⁇ m) to about 10 mil (254 ⁇ m), preferably from about 0.6 mil (15.2 ⁇ m) to about 2.5 mil (63.5 ⁇ m).
- Example 1 Preparation of the metallocene catalyst 3 kg of Sylopol 948 were placed in a process filter whose filter plate pointed downward and suspended in 15 L of toluene. 7 1 of 30%> strength by weight MAO solution (from Albemarle) were metered in while stining at such a rate that the internal temperature did not exceed 35°C. After stining for a further 1 hour at a low stiner speed, the suspension was filtered, firstly with no applied pressure and then under a nitrogen pressure of 3 bar.
- the outlet was subsequently closed, the filter cake was stined for 15 minutes and allowed to stand for 1 hour.
- the liquid was then pressed out from the filter cake by means of a nitrogen pressure of 3 bar with the outlet open.
- 15 L of isododecane were added to the solid which remained, the mixture was stined for 15 minutes and filtered.
- the washing step was repeated and the filter cake was subsequently pressed dry by means of a nitrogen pressure of 3 bar.
- the total amount of the catalyst was resuspended in 15 L of isododecane.
- the metallocene catalyst was metered in together with the Frisch propylene added to regulate the pressure. Triethylaluminum in the form of a 1 molar solution in heptane was likewise metered into the reactor.
- the propylene copolymer obtained in the first gas-phase reactor was transfened together with still active catalyst constituents into the second gas-phase reactor. There, the propylene-ethylene copolymer B was polymerized onto it at a total pressure, a temperature and a mean residence time as shown in Table 1. The ethylene concentration in the reaction gas was monitored by gas chromatography.
- the weight ratio of the propylene copolymer A formed in the first reactor [A(I)] to the propylene copolymer B formed in the second reactor [B(II)] is shown in Table 1.
- Isopropanol in the form of a 0.5 molar solution in heptane
- the weight ratio of the polymer formed in the first reactor to that formed in the second reactor was controlled by means of isopropanol which was metered into the second reactor in the form of a 0.5 molar solution in heptane and is shown in Table 1.
- hydrogen was metered into the second reactor as necessary.
- the proportion of propylene-ethylene copolymer B formed in the second reactor is given by the difference of amount transferred and amount discharged according to the relationship (output from second reactor - output from first reactor)/output from second reactor.
- Standard 1/h standard liters per hour
- the polymer powder obtained in the polymerization was admixed with a standard additive mixture in the granulation step.
- Granulation was canied out using a twin-screw extruder ZSK 30 from Werner & Pfleiderer at a melt temperature of 250°C.
- the propylene copolymer composition obtained contained 0.04% by weight of Irganox 1010 (from Ciba Specialty Chemicals), 0.07%> by weight of Irgafos 168, (from Ciba Specialty Chemicals), and 0.04% by weight of calcium stearate.
- the properties of the propylene copolymer composition are shown in Tables 2 and 3. The data were determined on the propylene copolymer composition after addition of additives and granulation or on test specimens produced therefrom.
- the suspension was heated to 50°C D 0.2°C over a period of 20-25 minutes while stining and stined for a further 2 hours at this temperature.
- the suspension was filtered through a glass frit which had been preheated to 50°C.
- About 350 g of the filtrate were weighed into an evaporator flask which had previously been dried over P 2 O 5 in a desiccator for 12 hours.
- the filtrate was evaporated to about 20-30 ml at 60°C under reduced pressure on a rotary evaporator.
- the solution was transfened quantitatively with the aid of several rinses with warm hexane into a 200 ml evaporating basin which had previously been dried over P 2 O 5 in a desiccator for 12 hours and weighed.
- the solution was evaporated to dryness on a hotplate while passing nitrogen over it. After evaporation, the evaporating basin was dried over P 2 O 5 at 200 mbar in a desiccator for 12 hours, weighed and the extraction residue was determined.
- the same procedure was repeated without addition of polymer granules and the residue in pure n-hexane was determined. The residue in pure n-hexane was subtracted to determine the proportion of material which is extracted by n-hexane.
- the brittle/tough transition was determined by means of the puncture test described in ISO 6603-2/40/20/C/4.4.
- the velocity of the punch was chosen as 4.4 m/s
- the diameter of the support ring was 40 mm
- the diameter of the impact ring was 20 mm.
- the test specimen was clamped in.
- the test specimen geometry was 6 cm D 6 cm at a thickness of 2 mm. To determine the temperature dependence curve, measurements were canied out at steps of 2°C in the temperature range from 26°C to -35°C using a test specimen preheated/precooled to the respective temperature.
- the brittle/tough transition was determined from the total deformation in mm defined as the displacement through which the punch has traveled when the force has passed through a maximum and dropped to 3% of this maximum force.
- the brittle/tough transition temperature is defined as the temperature at which the total deformation is at least 25% below the mean total deformation of the preceding 5 measurement points.
- the determination of the Haze values was canied out in accordance with the standard ASTM D 1003.
- the test specimens were injection-molded plates having an edge length of 6 x 6 cm and a thickness of 1 mm.
- the test specimens were injection molded at a melt temperature of 250°C and a tool surface temperature of 30°C.
- test specimens were clamped into the clamping device in front of the inlet orifice of a Hazegard System XL 211 from Pacific Scientific and the measurement was subsequently canied out. Testing was canied out at 23 °C, with each test specimen being examined once in the middle. To obtain a mean, 5 test specimens were tested in each case.
- the stress whitening behavior was assessed by means of the domed method. In the dome method, the stress whitening was determined by means of a falling dart apparatus as specified in DIN 53443 Part 1 using a falling dart having a mass of 250 g, a punch diameter of 5 mm and a dome radius of 25 mm. The drop was 50 cm.
- test specimen use was made of an injection-molded circular disk having a diameter of 60 mm and a thickness of 2 mm.
- the test specimen was injection molded at a melt temperature of 250°C and a tool surface temperature of 30°C. Testing was carried out at 23°C, with each test specimen being subjected to only one impact test.
- the test specimen was first laid on a support ring without being clamped and the falling dart was subsequently released. To obtain the mean, at least five test specimens were tested.
- the diameter of the visible stress whitening region is reported in mm and was determined by measuring this region in the flow direction and perpendicular thereto on the side of the circular disk opposite that on which impact occurs and forming the mean of the two values.
- the C 2 content of the propylene-ethylene copolymers was determined by means of IR spectroscopy.
- the structure of the propylene-ethylene copolymer B was determined by means of 13 C-NMR spectroscopy.
- the tensile E modulus was measured in accordance with ISO 527-2:1993.
- the test specimen of type 1 having a total length of 150 mm and a parallel section of 80 mm was injection molded at a melt temperature of 250°C and a tool surface temperature of 30°C. To allow after-crystallization to occur, the test specimen was stored for 7 days under standard conditions of 23°C/50% atmospheric humidity.
- a test unit model Z022 from Zwick-Roell was used for testing.
- the displacement measurement system in the determination of the E modulus had a resolution of 1 ⁇ m.
- the testing velocity in the determination of the E modulus was 1 mm/min, otherwise 50 mm/min.
- the yield point in the determination of the E modulus was in the range 0.05%>-0.25%.
- the determination of the melting point was canied out by means of DSC (differential scanning calorimetry). The measurement was canied out in accordance with ISO standard 3146 using a first heating step at a heating rate of 20°C per minute up to 200°C, a dynamic crystallization at a cooled rate of 20°C per minute down to 25°C and a second heating step at a heating rate of 20°C per minute back up to 200°C.
- the melting point is then the temperature at which the enthalpy versus temperature curve measured during the second heating step displays a maximum.
- the determination of the molar mass M n and the molar mass distribution M w /M n was canied out by gel permeation chromatography (GPC) at 145°C in 1,2,4- trichlorobenzene using a GPC apparatus model 150C from Waters. The data were evaluated by means of the Win-GPC software from HS-Entwicklungsgesellschaft fur letone Hard- und Software mbH, Ober-Hilbersheim. The columns were calibrated by means of polypropylene standards having molar masses from 100 to 10 g/mol.
- Comparative Example 2 was produced using a Ziegler Natta catalyst, and is a heterophasic copolymer of propylene with an ethylene content of 8.9 wt%>, a xylene solubles content of about 11.5 wt%>, and a MFR of 4.0, commercially available from Basell
- the weight percent of olefin polymer soluble in xylene at room temperature was determined by dissolving 2.5 g of polymer in 250 ml of xylene at room temperature in a vessel equipped with a stiner, and heating at 135°C with agitation for 20 minutes. The solution was cooled to 25°C while continuing the agitation, and then left to stand without agitation for 30 minutes so that the solids could settle. The solids were filtered with filter paper, the remaining solution was evaporated by treating it with a nitrogen stream, and the solid residue is vacuum dried at 80°C until a constant weight is reached.
- the polymer sample also contained 0.05 wt% of calcium stearate, 0.06 wt%> of Irganox 1010 commercially available from Ciba Specialty Chemicals Corporation, and 0.06 wt% of Irgafos 168 commercially available from Ciba Specialty Chemicals Corporation.
- Comparative Example 3 Comparative Example 3 was produced using a Ziegler Natta catalyst and comprises 70 wt% of a propylene random copolymer having 2.7 wt%> ethylene, and 30 wt% of an ethylene/propylene rubber containing 60 wt% of ethylene and 40 wt%> propylene, commercially available from Basell USA Inc.
- the total composition has an ethylene content of 22 wt%, a xylene solubles content of about 31 wt%, measured as described above for Example 1 , and a MFR of 9.5.
- the sample also contained 0.1 wt% of Irganox 1010, commercially available from Ciba Specialty Chemicals Corporation and 0.03 wt%> of DHT-4A commercially available from Kyowa Chemical Ind. Co. Ltd.
- Comparative Example 4 Comparative Example 4 was produced using a Ziegler Natta catalyst and is a random copolymer of propylene with a butene content of about 11.5 wt%, and a MFR of 5.5, commercially available from Basell USA Inc.
- the sample also contained 0.05 wt% of Irganox 1010, commercially available from Ciba Specialty Chemicals Corporation, 0.10 wt% Irgafos 168, commercially available from Ciba Specialty Chemicals Corporation, and 0.025 wt% DHT-4A commercially available from Kyowa Chemical Ind. Co. Ltd.
- Comparative Example 5 Comparative Example 5 was produced using a Ziegler Natta catalyst and is a heterophasic copolymer of propylene with an ethylene content of 18.3 wt% and a xylene solubles content of about 19 wt%, measured as described above for Example 1, and a MFR of 4.0, commercially available from Basell USA Inc.
- the sample also contained 0.05 wt%> calcium stearate, 0.06 wt%o of Irganox 1010 commercially available from Ciba Specialty Chemicals Corporation, 0.6 wt% of Irgafos 168 commercially available from Ciba Specially Chemicals Corporation and 0.25 wt% DSTDP commercially available from Cytec Industries.
- Comparative Example 6 Comparative Example 6 was produced using a Ziegler Natta catalyst and is a propylene homopolymer having a 12 MFR and a xylene solubles content of about 4 wt%, measured as described above for Example 1, commercially available from Basell USA Inc.
- the sample also contained 0.06 wt% calcium stearate, 0.075 wt% of Irganox 1010 commercially available from Ciba Specialty Chemicals Corporation and 0.075 wt% of Irgafos 168, commercially available from Ciba Specialty Chemicals Corporation.
- Comparative Example 7 Comparative Example 7 was produced using a Ziegler Natta catalyst and is a random copolymer of propylene with an ethylene content of about 3.2 wt%, an MFR of 6 and a xylene solubles content of about 6.2 wt%>, measured as described above for Example 1 , commercially available from Basell USA Inc.
- the sample also contained 0.05 wt calcium stearate, 0.06 wt% of Irganox 1010, commercially available from Ciba Specialty Chemicals Corporation, 0.06 wt% of Irganox 168 commercially available from Ciba Specialty Chemicals Corporation, 0.075 wt%> erucamide, commercially available from Crompton Corporation, and 0.1 wt% of SiO2 concentrate (10811235) commercially available from Clariant International Ltd .
- Cast films of 1 mil (25.4 ⁇ m) were prepared from the polymers of Example 1 and Comparative Examples 2-7. The film extrusion was conducted on the Gloucester Battenfeld Cast Film Extruder, commercially available from Battenfeld Gloucester Engineering Co., Inc.
- the die was made by Cloeren Incorporated and was equipped with a vacuum device as well as the air knife and static edge pinners to enhance film quenching.
- the die had an A/B/C type coextrusion feedblock. Properties of the 1 mil (25.4 ⁇ m) film samples prepared from Example 1 and
- Table 5 summarizes vapor transmission testing, and xylene and hexane solubles tests performed on the films of Example 1 and Comparative Examples 2, 4, 6, and 7.
- the films of the invention possess low hexane extractables and xylene solubles, as well as improved vapor transmission properties relative to comparative examples 2, 4, 6 and 7.
- the films of the invention also demonstrate good hot tack and heat seal strength.
- Hot tack is a measurement of the strength of seals immediately after a seal has been made and before it cools to ambient temperature.
- Heat seal strength is a measurement of the strength of heat seals performed after the seal has been conditioned.
- films of Example 1 and Comparative Examples 2-7 were tested using a JB/Topwave Hot tack tester according to a modified ASTM F 1921-98 procedure. The instrument heat sealed each of the films and immediately measured the strength of the hot seal after conclusion of the sealing time.
- the seal pressure was 0.5 N/mm 2 , with a seal time of 0.50 seconds, cooling time of 0.5 seconds, peel speed of 150 mm/s, and sample width 25 mm.
- the sealing was done over a range of temperatures.
- Figure 1 illustrates hot tack curves showing force requirements versus temperature for Example 1 and Comparative Examples 2-7. As shown in Figure 1, the film of the invention demonstrates improved hot tack characteristics over Comparative Example 2 and Comparative Examples 5-7.
- the heat seal strength of films of Example 1 and Comparative Examples 2-7 was measured by first conditioning the films for over 24 hours at 50%> relative humidity and 23°C. Heat sealing was performed using a Sentinel heat sealer at 275 kPa, and 0.5 second dwell time.
- Figure 2 illustrates heat seal curves showing peel force versus temperature for Example 1 and Comparative Examples 2-7. As shown in Figure 2, the film of the invention demonstrates improved heat seal characteristics over Comparative Examples 2-3, and 5-6, and equal to better performance heat seal characteristics over Comparative Example 7.
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Abstract
Description
Claims
Priority Applications (2)
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EP05731302A EP1730231B1 (en) | 2004-03-24 | 2005-03-21 | Flexible propylene copolymer compositions having a high transparency |
US10/593,791 US20070155921A1 (en) | 2004-03-24 | 2005-03-21 | Flexible prolylene copolymer compositions having a high transparency |
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EP04101224 | 2004-03-24 | ||
EP04101224.6 | 2004-03-24 | ||
US61078504P | 2004-09-17 | 2004-09-17 | |
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US (1) | US20070155921A1 (en) |
EP (1) | EP1730231B1 (en) |
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WO (1) | WO2005090467A1 (en) |
Cited By (8)
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EP2335489A3 (en) * | 2009-12-17 | 2011-07-06 | CSK Food Enrichment B.V. | Method for ripening a cheese |
WO2012084768A1 (en) * | 2010-12-21 | 2012-06-28 | Basell Polyolefine Gmbh | Polypropylene composition with high elasticity and transparency |
EP2686382B1 (en) | 2011-03-18 | 2016-08-10 | INEOS Manufacturing Belgium NV | Propylene-ethylene random copolymer |
EP2898017B1 (en) | 2012-09-19 | 2017-03-29 | Ineos Europe AG | Propylene-ethylene random copolymer |
WO2019052821A1 (en) * | 2017-09-14 | 2019-03-21 | Basell Poliolefine Italia S.R.L. | Permeable polymer film |
WO2020076505A1 (en) * | 2018-10-10 | 2020-04-16 | Exxonmobil Chemical Patents Inc. | Polypropylene for films |
WO2020012300A3 (en) * | 2018-07-11 | 2020-04-30 | Nova Chemicals (International) S.A. | Polyethylene composition and film having high stiffness, outstanding sealability and high permeability |
CN113840846A (en) * | 2019-05-29 | 2021-12-24 | 博里利斯股份公司 | C2C3Random copolymer composition |
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EP1871832B1 (en) * | 2005-04-21 | 2012-06-13 | Basell Poliolefine Italia S.r.l. | Biaxially oriented propylene polymer films |
US20090017710A1 (en) * | 2006-02-02 | 2009-01-15 | Basell Polyolefine Gmbh | Propylene Melt Blown Resins, Propylene Melt Blown Resin Fibers and Non-Woven Fabric Made From the Same, and Methods of Making the Same |
CN102604345A (en) * | 2012-02-28 | 2012-07-25 | 深圳市光华伟业实业有限公司 | Transparent wear-resisting plastic alloy and preparation method thereof |
ES2601456T3 (en) * | 2012-05-18 | 2017-02-15 | Borealis Ag | Molded article with enhanced tension whitening |
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 |
WO2014154610A1 (en) | 2013-03-26 | 2014-10-02 | Borealis Ag | Propylene copolymer with high impact properties |
DE102015006489A1 (en) * | 2015-05-22 | 2016-11-24 | Kocher-Plastik Maschinenbau Gmbh | Plastic container product |
CN111961027B (en) * | 2020-08-18 | 2023-11-17 | 上海齐润新材料有限公司 | Composition and method for preparing transparent articles at low temperature |
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Also Published As
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EP1730231A1 (en) | 2006-12-13 |
CN1957036A (en) | 2007-05-02 |
CN100558807C (en) | 2009-11-11 |
US20070155921A1 (en) | 2007-07-05 |
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