EP3902850A1 - A process for producing polyolefin film composition and films prepared thereof - Google Patents
A process for producing polyolefin film composition and films prepared thereofInfo
- Publication number
- EP3902850A1 EP3902850A1 EP19828782.3A EP19828782A EP3902850A1 EP 3902850 A1 EP3902850 A1 EP 3902850A1 EP 19828782 A EP19828782 A EP 19828782A EP 3902850 A1 EP3902850 A1 EP 3902850A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ethylene
- copolymer
- polymer mixture
- polymerisation
- ethylene polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 156
- 238000000034 method Methods 0.000 title claims abstract description 65
- 230000008569 process Effects 0.000 title claims abstract description 47
- 229920000098 polyolefin Polymers 0.000 title description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000005977 Ethylene Substances 0.000 claims abstract description 144
- 229920000573 polyethylene Polymers 0.000 claims abstract description 97
- 229920001577 copolymer Polymers 0.000 claims abstract description 72
- 239000000155 melt Substances 0.000 claims abstract description 49
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229920002959 polymer blend Polymers 0.000 claims abstract description 46
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 30
- 239000004711 α-olefin Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 238000000071 blow moulding Methods 0.000 claims abstract description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 42
- 101100023124 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfr2 gene Proteins 0.000 claims description 34
- 239000002002 slurry Substances 0.000 claims description 33
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 50
- 239000007789 gas Substances 0.000 description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 27
- 239000001257 hydrogen Substances 0.000 description 27
- 229910052739 hydrogen Inorganic materials 0.000 description 27
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- -1 polyethylene Polymers 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 239000012530 fluid Substances 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000004411 aluminium Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 5
- 230000002902 bimodal effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003701 inert diluent Substances 0.000 description 5
- 229920000092 linear low density polyethylene Polymers 0.000 description 5
- 239000004707 linear low-density polyethylene Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N (3S)-octan-3-ol Natural products CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 1
- WOFPPJOZXUTRAU-UHFFFAOYSA-N 2-Ethyl-1-hexanol Natural products CCCCC(O)CCC WOFPPJOZXUTRAU-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- ONJXMLOOLFUVAT-UHFFFAOYSA-N C(=CC(C)=C)[AlH2] Chemical compound C(=CC(C)=C)[AlH2] ONJXMLOOLFUVAT-UHFFFAOYSA-N 0.000 description 1
- 241000252095 Congridae Species 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 239000002656 Distearyl thiodipropionate Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)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 BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- GMNSEICSYCVTHZ-UHFFFAOYSA-N dimethylalumanyloxy(dimethyl)alumane Chemical compound C[Al](C)O[Al](C)C GMNSEICSYCVTHZ-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 235000019305 distearyl thiodipropionate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010096 film blowing Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- KXDANLFHGCWFRQ-UHFFFAOYSA-N magnesium;butane;octane Chemical compound [Mg+2].CCC[CH2-].CCCCCCC[CH2-] KXDANLFHGCWFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 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
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- OOZBTDPWFHJVEK-UHFFFAOYSA-N tris(2-nonylphenyl) phosphate Chemical compound CCCCCCCCCC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC OOZBTDPWFHJVEK-UHFFFAOYSA-N 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- 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
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention is directed to a method for producing multimodal ethylene polymer film compositions and films prepared thereof. Especially, the present invention is directed to a method for making multimodal ethylene copolymer film composition by a process comprising polymerizing ethylene in at least three polymerization stages. Further, the present invention is directed to films comprising the multimodal ethylene copolymer composition produced by the method comprising at least three polymerization stages. Further, the invention is directed to the use of such multimodal ethylene copolymer compositions for making films with improved processability and throughput.
- WO-A-2004000902 discloses bimodal low density PE resins. The document does not disclose multimodal ethylene polymer composition produced in three polymerisation stage.
- EP-A-2067799 discloses multimodal LLDPE resins which have been produced in two polymerization stages in a loop and a gas phase reactor in the presence of a ligand-modified catalyst. The document does not disclose a third polymerization stage.
- EP-A-2246369 discloses LLDPE produced in the presence of a Ziegler-Natta catalyst with specific halogenated aluminium alkyl compounds as a cocatalyst. While the document briefly refers to two-stage polymerization its examples are one-stage polymerization runs. The document does not disclose any three-stage polymerization.
- EP-A-2246372 discloses LLDPE produced in the presence of a Ziegler-Natta catalyst with a halogenated aluminium alkyl compounds as a cocatalyst.
- the document discloses ethylene copolymerisation in two-stage polymerization configuration. It’s only generally mentioned that optionally additional reactors may be used. It does not, however, disclose the nature of the polymers produced in such stages and it exemplifies only two-stage polymerization.
- EP-A-2228394 discloses LLDPE polymers produced in two polymerization stages using amulticomponent catalyst comprising titanium and vanadium compounds.
- the document discloses that it is possible to include further polymerization stages, such as a third and a fourth polymerization stage which are preferably conducted in gas phase. It does not, however, disclose the nature of the polymers produced in such stages and it exemplifies only two-stage polymerization.
- EP-A-2186833 discloses a three-stage polymerization in a cascaded reactor sequence of two loop reactors followed by a gas phase reactor.
- a polymer having an M FR 2 of preferably 200 to 1000 g/10 min and a density of preferably 945 to 978 kg/m 3 is produced in the first stage.
- the polymer produced in the second stage is disclosed to have an MFR 2 of preferably 200 to 1000 g/10 min and a density of preferably 945 to 978 kg/m 3 .
- the final polymer had an MFR 21 of preferably 5 to 30 g/10 min and a density of preferably 940 to 970 kg/m 3 .
- the polymers produced in the first and second stages had the same MFR 2 .
- the polymers produced in the first two stages were homopolymers and the final resins had MFR 5 of from 0.2 to 0.4 g/10 min and density of about 955 kg/m 3 .
- EP2415598 discloses a multilayer film comprising at least one layer of a multimodal terpolymer, e.g. a bimodal linear low density ethylene/1 -butene/C6-Ci2-alpha-olefin terpolymer.
- the multimodal polymer comprises a low molecular weight component corresponding ethylene homopolymer or a low molecular weight ethylene copolymer and a high molecular weight component corresponding to ethylene terpolymer with higher alpha-olefin comonomers.
- the low molecular weight component is an ethylene homoplymer and the high molecular weight component is ethylene/1 -butene/1 -hexene terpolymer.
- the multimodal terpolymer is produced in a two stage polymerisation process. Final densities are disclosed to be in the range of 910 - 950 kg/m 3 or 935 - 970 kg/m 3 or 900 - 935 kg/m 3 ; and MFR21 (190 °C, 21 ,6 kg load, IS01133) 7 to 60 g/10min or 2 to 35 g/10min or 15 to 80 g/10min, respectively.
- WO 2015/086812 (EP2883887) describes a process for making multimodal ethylene copolymers where the method comprises polymerising ethylene and comonomers in three polymerisation stages, and further use of said copolymers for making films.
- the ethylene copolymer produced according to the process has the density of 906 to 925 kg/m 3 and MFR 5 (190 °C, 5,0 kg load, IS01133) of 0,5 to 5,0 g/10 min.
- the copolymer produced in the first polymerisation stage and the first copolymer mixture being a mixture of the first polymer and polymer produced in the second stage have claimed densities in the range of 945 to 955 kg/m 3 and melt flow rates MFR 2 in the range of 150 to 1000 kg/m 3 .
- EP2883885 describes similar type of polymers as described in WO 2015/086812.
- bimodal ethylene polymers have desired properties for different application needs. Suitable densities and melt flow rates are normal decisive features of polyethylene film materials.
- Such bimodal terpolymers are known in the state of the art and are described e.g. in WO 03/066698 or WO 2008/034630 or are commercially available, such as BorShapeTM FX1001 and BorShapeTM FX1002 (both from Borealis AG, Vienna, Austria).
- the present invention therefore provides especially for example good mechanical properties, such as for example DDI and/or tear, of polymer film composition and/or good processability and/or high throughput in a film making process.
- the present invention concerns a process for producing multimodal ethylene polymer film compositions comprising the steps of
- PE1 ethylene homo- or copolymer having a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m 3 ;
- first ethylene polymer mixture comprising the first ethylene homo- or copolymer and a second ethylene copolymer, said first ethylene polymer mixture having a density of from 940 to 980 kg/m 3 and a melt flow rate MFR2 of from 100 to 600 g/10 min, and wherein the MFR2 0f the first ethylene homo- or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1) and the second ethylene homo- or copolymer (PE2) has a melt flow rate MFR2 of from 400 to 2000 g/10min and optionally a density of from 940 to 980 kg/m 3 ; and
- the present process for producing polyethylene film composition comprises polymerisation of ethylene and at least one a-olefin in multiple polymerisation steps in the presence of a polymerisation catalyst.
- multiple polymerisation steps mean a process comprising at least three polymerisation steps.
- the at least one a-olefin one alpha-olefin comonomer may be selected from a-olefins having from 4 to 10 carbon atoms and their mixtures. Especially suitable a-olefins are those having from 4 to 8 carbon atoms, including their mixtures. In particular 1-butene, 1-hexene and 1- octene and their mixtures are the preferred a-olefins.
- the a-olefin used in the different polymerisation steps may be the same or different.
- the polymerisation steps may be connected in any order, i.e. the first polymerisation step may precede the second polymerisation step, or the second polymerisation step may precede the first polymerisation step or, alternatively, polymerisation steps may be connected in parallel. However, it is preferred to operate the polymerisation steps in cascaded mode.
- the polymerisation is conducted in the presence of an olefin polymerisation catalyst.
- the catalyst may be any catalyst which is capable of producing all components of the multimodal ethylene copolymer. Suitable catalysts are, among others, Ziegler - Natta catalysts based on a transition metal, such as titanium, zirconium and/or vanadium or metallocene catalysts or late transition metal catalysts, as well as their mixtures. Especially Ziegler - Natta catalysts are useful as they can produce polymers within a wide range of molecular weight and other desired properties with a high productivity. Ziegler - Natta catalysts used in the present invention are supported on an external support.
- Suitable Ziegler - Natta catalysts preferably contain a magnesium compound, an aluminium compound and a titanium compound supported on a particulate support.
- the particulate support typically used in Ziegler-Natta catalysts comprises an inorganic oxide support, such as silica, alumina, titania, silica-alumina and silica-titania or a MgCh based support.
- the catalyst used in the present invention is supported on an inorganic oxide support. Most preferably the Ziegler-Natta catalyst used in the present invention is supported on silica.
- the average particle size of the silica support can be typically from 10 to 100 mhi. However, it has turned out that special advantages can be obtained if the support has an average particle size from 15 to 30 mhi, preferably from 18 to 25 mhi. Alternatively, the support may have an average particle size of from 30 a 80 mhi, preferably from 30 to 50 mhi. Examples of suitable support materials are, for instance, ES747JR produced and marketed by Ineos Silicas (former Crossfield), and SP9-491 , produced and marketed by Grace.
- the magnesium compound is a reaction product of a magnesium dialkyl and an alcohol.
- the alcohol is a linear or branched aliphatic monoalcohol. Preferably, the alcohol has from 6 to 16 carbon atoms. Branched alcohols are especially preferred, and 2-ethyl-1-hexanol is one example of the preferred alcohols.
- the magnesium dialkyl may be any compound of magnesium bonding to two alkyl groups, which may be the same or different. Butyl-octyl magnesium is one example of the preferred magnesium dialkyls.
- aluminium compound is chlorine containing aluminium alkyl.
- Especially preferred compounds are aluminium alkyl dichlorides, aluminium dialkyl chlorides and aluminium alkyl sesquichlorides.
- the transition metal is preferably titanium.
- the titanium compound is a halogen containing titanium compound, preferably chlorine containing titanium compound.
- Especially preferred titanium compound is titanium tetrachloride.
- the catalyst can be prepared by sequentially contacting the carrier with the above mentioned compounds, as described in EP-A-688794 or WO-A-99/51646. Alternatively, it can be prepared by first preparing a solution from the components and then contacting the solution with a carrier, as described in WO-A-01/55230.
- the Ziegler - Natta catalyst is used together with an activator, which is also called as cocatalyst.
- Suitable activators are metal alkyl compounds, typically Group 13 metal alkyl compounds, and especially aluminium alkyl compounds. They include trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, tri-isobutylaluminium,
- Aluminium alkyl compounds may also include alkyl aluminium halides, such as ethylaluminium dichloride, diethylaluminium chloride,
- ethylaluminium sesquichloride dimethylaluminium chloride and the like and alkylaluminium oxy- compounds, such as methylaluminiumoxane, hexaisobutylaluminiumoxane and
- isoprenylaluminium isoprenylaluminium.
- cocatalysts are trialkylaluminiums, of which
- triethylaluminium, trimethylaluminium and tri-isobutylaluminium are particularly preferred.
- the amount in which the activator is used depends on the specific catalyst and activator.
- triethylaluminium is used in such amount that the molar ratio of aluminium to the transition metal, like Al/Ti, is for example from 1 to 1000, preferably from 3 to 100 and in particular from about 5 to about 30 mol/mol.
- the process may comprise a prepolymerisation step preceding the actual polymerisation steps.
- the purpose of the prepolymerisation is to polymerise a small amount of polymer onto the catalyst at a low temperature and/or a low monomer concentration. By prepolymerisation it is possible to improve the performance of the catalyst in slurry and/or modify the properties of the final polymer.
- the prepolymerisation step is conducted in slurry.
- the prepolymerisation step may be conducted in a loop reactor.
- the prepolymerisation is then preferably conducted in an inert diluent, typically a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes etc., or their mixtures.
- diluent is a low-boiling hydrocarbon having from 1 to 4 carbon atoms or a mixture of such hydrocarbons.
- the temperature in the prepolymerisation step is typically from 0 to 90 °C, preferably from 20 to 80 °C and more preferably from 55 to 75 °C.
- the pressure is not critical and is typically from 1 to 150 bar, preferably from 40 to 80 bar.
- the amount of monomer is typically such that from about 0.1 to 1000 grams of monomer per one gram of solid catalyst component is polymerised in the prepolymerisation step.
- prepolymerisation reactor do not all contain the same amount of prepolymer. Instead, each particle has its own characteristic amount which depends on the residence time of that particle in the prepolymerisation reactor. As some particles remain in the reactor for a relatively long time and some for a relatively short time, then also the amount of prepolymer on different particles is different and some individual particles may contain an amount of prepolymer which is outside the above limits. However, the average amount of prepolymer on the catalyst typically is within the limits specified above.
- the molecular weight of the prepolymer may be controlled by hydrogen as it is known in the art. Further, antistatic additive may be used to prevent the particles from adhering to each other or the walls of the reactor, as disclosed in WO-A-96/19503 and WO-A-96/32420.
- the catalyst components are preferably all (separately or together) introduced to the
- the amounts of hydrogen and comonomer are adjusted so that the presence of the prepolymer has no effect on the properties of the final multimodal polymer.
- melt flow rate of the prepolymer is greater than the melt flow rate of the final polymer but smaller than the melt flow rate of the polymer produced in the first polymerisation stage.
- density of the prepolymer is greater than the density of the final polymer.
- the density is approximately the same as or greater than the density of the polymer produced in the first polymerisation stage.
- the amount of the prepolymer is not more than about 5 % by weight of the multimodal polymer comprising the prepolymer.
- the first polymerisation step typically operates at a temperature of from 20 to 150 °C, preferably from 50 to 110 °C and more preferably from 60 to 100 °C.
- the polymerisation may be conducted in slurry, gas phase or solution.
- the first homo- or copolymer of ethylene is produced.
- the first ethylene homo-or copolymer has a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m 3 .
- the catalyst may be transferred into the first polymerisation step by any means known in the art. It is thus possible to suspend the catalyst in a diluent and maintain it as homogeneous slurry. Especially preferred it is to use oil having a viscosity form 20 to 1500 mPa-s as diluent, as disclosed in WO-A-2006/063771. It is also possible to mix the catalyst with a viscous mixture of grease and oil and feed the resultant paste into the first polymerisation step. Further still, it is possible to let the catalyst settle and introduce portions of thus obtained catalyst mud into the first polymerisation step in a manner disclosed, for instance, in EP-A-428054.
- the first polymerisation step may also be preceded by a prepolymerisation step, in which case the mixture withdrawn from the prepolymerisation step is directed into the first polymerisation step.
- the a-olefin Into the first polymerisation step ethylene, the a-olefin, optionally an inert diluent, and optionally hydrogen are introduced. Hydrogen and the a-olefin are introduced in such amounts that the melt flow rate MFR2 and the density of the first ethylene homo-or copolymer are in the desired values.
- a-olefin or the alpha-olefin comonomer (these terms may be used interchangeably herein) is as defined above having from 4 to 10 carbon atoms and their mixtures, and especially suitable a-olefins are those having from 4 to 8 carbon atoms, including their mixtures. In particular 1 -butene, 1 -hexene and 1-octene and their mixtures are the preferred a-olefins.
- the polymerisation of the first polymerisation step may be conducted in slurry. Then the polymer particles formed in the polymerisation, together with the catalyst fragmented and dispersed within the particles, are suspended in the fluid hydrocarbon. The slurry is agitated to enable the transfer of reactants from the fluid into the particles.
- the polymerisation usually takes place in an inert diluent, typically a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes etc., or their mixtures.
- a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes etc., or their mixtures.
- the diluent is a low-boiling hydrocarbon having from 1 to 4 carbon atoms or a mixture of such hydrocarbons.
- An especially preferred diluent is propane, possibly containing minor amount of methane, ethane and/or butane.
- the ethylene content in the fluid phase of the slurry may be from 1 to about 50 % by mole, preferably from about 1.5 to about 20 % by mole and in particular from about 2 to about 15 % by mole.
- the benefit of having a high ethylene concentration is that the productivity of the catalyst is increased but the drawback is that more ethylene then needs to be recycled than if the concentration was lower.
- the slurry polymerisation may be conducted in any known reactor used for slurry
- Such reactors include a continuous stirred tank reactor and a loop reactor. It is especially preferred to conduct the polymerisation in loop reactor. In such reactors the slurry is circulated with a high velocity along a closed pipe by using a circulation pump. Loop reactors are generally known in the art and examples are given, for instance, in US-A-4582816, US-A- 3405109, US-A-3324093, EP-A-479186 and US-A-5391654.
- the first ethylene homo-or copolymer is produced in conditions where the ratio of the a-olefin to ethylene is not more than about 400 mol/kmol, such as not more than 300 mol/kmol, then it is usually advantageous to conduct the slurry polymerisation above the critical temperature and pressure of the fluid mixture. Such operation is described in US-A-5391654.
- the polymerisation in the first polymerisation step is conducted as slurry polymerisation the polymerisation in the first polymerisation step is conducted at a temperature within the range of from 50 to 115 °C, preferably from 70 to 110 °C and in particular from 80 to 105 °C.
- the pressure in the first polymerisation step is then from 1 to 300 bar, preferably from 40 to 100 bar.
- the amount of hydrogen is adjusted based on the desired melt flow rate of the first ethylene homo-or copolymer and it depends on the specific catalyst used.
- the molar ratio of hydrogen to ethylene is for example from 10 to 2000 mol/kmol, preferably from 20 to 1000 mol/kmol and in particular from 40 to 800 mol/kmol.
- the amount of the a-olefin is adjusted based on the desired density of the first ethylene homo- or copolymer and it, too, depends on the specific catalyst used.
- the molar ratio of the a-olefin to ethylene is for example from 100 to 1000 mol/kmol, preferably from 150 to 600 mol/kmol.
- the polymerisation of the first polymerisation step may also be conducted in gas phase.
- a preferable embodiment of gas phase polymerisation reactor is a fluidised bed reactor. There the polymer particles formed in the polymerisation are suspended in upwards moving gas. The gas is introduced into the bottom part of the reactor. The upwards moving gas passes the fluidised bed wherein a part of the gas reacts in the presence of the catalyst and the unreacted gas is withdrawn from the top of the reactor. The gas is then compressed and cooled to remove the heat of polymerisation. To increase the cooling capacity it is sometimes desired to cool the recycle gas to a temperature where a part of the gas condenses. After cooling the recycle gas is reintroduced into the bottom of the reactor.
- Fluidised bed polymerisation reactors are disclosed, among others, in US-A-4994534, US-A-4588790, EP-A-699213, EP-A-628343, FI-A-921632, FI-A-935856, US-A-4877587, FI-A-933073 and EP-A-75049.
- the polymerisation of the first polymerisation step is conducted in slurry.
- the polymerisation is conducted at a temperature exceeding the critical temperature of the fluid mixture and pressure exceeding the critical pressure of the fluid mixture.
- At least one a-olefin may be present in the first polymerisation step, where the polymer produced in the first step is the first ethylene homo- or copolymer.
- the density of the first ethylene homo-or copolymer is for example from 940 to 980 kg/m 3 .
- the polymerisation is preferably conducted as a slurry polymerisation in liquid diluent at a
- the molar ratio of the a-olefin to ethylene may be for example from 100 to 1000 mol/kmol, and preferably from 150 to 600 mol/kmol.
- the polymerisation rate in the first polymerisation step is suitably controlled to achieve the desired amount of the first ethylene homo-or copolymer in the second ethylene polymer mixture.
- the second ethylene polymer mixture contains from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to ⁇ 25 % by weight of the first ethylene homo- or copolymer.
- the polymerisation rate is suitably controlled by adjusting the ethylene
- the concentration in the first polymerisation step is suitably for example from 0.5 to 10 % by mole and preferably from 1 to 8 % by mole.
- the molar ratio of hydrogen to ethylene is suitably from 50 to 350 mol/kmol, preferably from 75 to 325 mol/kmol and in particular from 100 to 300 mol/kmol in the first polymerisation step.
- the second homo- or copolymer of ethylene is produced in the second polymerisation step in the presence of the first homo- or copolymer of ethylene.
- the second polymerisation step typically operates at a temperature of from 20 to 150 °C, preferably from 50 to 110 °C and more preferably from 60 to 100 °C.
- the polymerisation may be conducted in slurry, gas phase or solution.
- the second homo- or copolymer of ethylene is produced in the presence of the first homo- or copolymer of ethylene.
- the first homo- or copolymer of ethylene (PE1) and the second homo- or copolymer of ethylene (PE2) together form the first ethylene polymer mixture (PEM1).
- the first ethylene polymer mixture has a density of from 940 to 980 kg/m 3 and a melt flow rate MFR2 of from 100 to 600 g/10 min.
- the first homo- or copolymer of ethylene (PE1) is transferred from the first polymerisation step to the second polymerisation step by using any method known to the person skilled in the art. If the first polymerisation step is conducted as slurry polymerisation in a loop reactor, it is advantageous to transfer the slurry from the first polymerisation step to the second
- ethylene optionally an inert diluent, and optionally hydrogen and/or the a-olefin are introduced. Hydrogen and the a-olefin, are introduced in such amounts that the melt flow rate MFR2 and the density of the first ethylene polymer mixture are within the desired values.
- the polymerisation of the second polymerisation step may be conducted in slurry in the same way as it was discussed above for the first polymerisation step.
- the amount of hydrogen in the second polymerisation step is adjusted based on the desired melt flow rate of the first ethylene polymer mixture and it depends on the specific catalyst used.
- the molar ratio of hydrogen to ethylene is for example from 100 to 2000 mol/kmol, preferably from 200 to 1000 mol/kmol and in particular from 250 to 800 mol/kmol.
- the amount of the a-olefin is adjusted based on the desired density of the first ethylene polymer mixture and it, too, depends on the specific catalyst used.
- the molar ratio of the a-olefin to ethylene is for example from 0 to 1000 mol/kmol, preferably from 0 to 800 mol/kmol and in particular from 0 to 700 mol/kmol.
- the polymerisation of the second polymerisation step may also be conducted in gas phase in the same way as was discussed above for the first polymerisation step.
- the second polymerisation step is conducted in slurry phase as described above.
- the molar ratio of hydrogen to ethylene is suitably from 350 to 600 mol/kmol, preferably from 375 to 550 mol/kmol and in particular from 400 to 500 mol/kmol in the second polymerisation step.
- the polymerisation is conducted at a temperature exceeding the critical temperature of the fluid mixture and pressure exceeding the critical pressure of the fluid mixture.
- the a-olefin is present in the first polymerisation step and in the second polymerisation step.
- the density of the first ethylene homo-or copolymer is controlled by the molar ratio of the a-olefin to ethylene in the first polymerisation step and the density of the first ethylene polymer mixture is controlled by the molar ratio of the a-olefin to ethylene in the second polymerisation step.
- the molar ratio of the a-olefin to ethylene may then be for example from 50 to 1000 mol/kmol, and preferably from 100 to 600 mol/kmol in the second polymerisation step.
- the a-olefin used in the second polymerisation step may be the same or different as used in the first polymerisation step.
- the polymerisation rate in the second polymerisation step is suitably controlled to achieve the desired amount of the second ethylene homo- or copolymer in the second ethylene polymer mixture.
- the second ethylene polymer mixture contains from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to ⁇ 25 % by weight of the second ethylene copolymer.
- the polymerisation rate is suitably controlled by adjusting the ethylene concentration in the second polymerisation step.
- the mole fraction of ethylene in the reaction mixture is suitably from 2 to 10 % by mole and preferably from 3 to 8 % by mole.
- the mole fraction of ethylene in % by mole in the reaction mixture in the second polymerisation step may thereby be lower than the mole fraction of ethylene in % by mole in the reaction mixture in the first polymerisation step.
- the melt flow rate MFR2 0f the first ethylene homo-or copolymer (PE1) is in the range 15 to 300 g/10 min and the melt flow rate MFR2 of the first ethylene homo-or copolymer mixture (PEM1) is in the range 100 to 600 g/10 min and MFR 2 (PE1) ⁇
- MFR 2 (PEM1). I.e. the MFR2 0f the polymer produced in the first reactor is lower than the polymer mixture produced in the second polymerisation reactor.
- the ratio of MFR 2 (PEM1)/MFR 2 (PE1) may be for example between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
- the second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture (PEM1) and the third ethylene copolymer (PE3) is formed.
- ethylene Into the third polymerisation step are introduced ethylene, at least one a-olefin having 4 to 10 carbon atoms, hydrogen and optionally an inert diluent.
- polymerisation step is conducted at a temperature within the range of from 50 to 100 °C, preferably from 60 to 100 °C and in particular from 70 to 95 °C.
- the pressure in the third polymerisation step is for example from 1 to 300 bar, preferably from 5 to 100 bar.
- the polymerisation in the third polymerisation step may be conducted in slurry.
- polymerisation may then be conducted along the lines as was discussed above for the first and second polymerisation steps.
- the amount of hydrogen in the third polymerisation step is adjusted for achieving the desired melt flow rate of the second ethylene polymer mixture.
- the molar ratio of hydrogen to ethylene depends on the specific catalyst used. For many generally used Ziegler - Natta catalysts the molar ratio of hydrogen to ethylene is for example from 0 to 50 mol/kmol, preferably from 3 to 35 mol/kmol.
- the ratio of the a-olefin (sum of a-olefins) to ethylene depends on the type of the catalyst and the type of the a-olefin. The ratio is typically for example from 100 to 1000 mol/kmol, preferably from 150 to 800 mol/kmol. If more than one a-olefin is used the ratio of the a-olefin to ethylene is the ratio of the sum of all the a-olefins to ethylene.
- the a-olefin used in the third polymerisation step may be the same or different as used in the previous polymerisation steps.
- the a-olefin is preferably an a-olefin of 4 to 8 carbon atoms or mixtures thereof.
- 1-butene, 1-hexene and 1-octene and their mixtures are the preferred a-olefins, especially preferred 1 -butene and 1 -hexene.
- the polymerisation in the third polymerisation step may be, and preferably is, conducted in gas phase.
- hydrogen is typically added in such amount that the ratio of hydrogen to ethylene is for example from 3 to 100 mol/kmol, preferably from 4 to 50 mol/kmol for obtaining the desired melt index of the second ethylene polymer mixture.
- the amount of a-olefin having from 4 to 10 carbon atoms is adjusted to reach the targeted density of the second ethylene polymer mixture.
- the ratio of the a-olefin to ethylene is typically from 100 to 1000 mol/kmol, preferably from 150 to 800 mol/kmol, further preferred ⁇ 150 to 300 mol/kmol. If more than one a-olefin is used the ratio of the a-olefin to ethylene is the ratio of the sum of all the a-olefins to ethylene.
- the gas phase reactor preferably is a vertical fluidised bed reactor. There the polymer particles formed in the polymerisation are suspended in upwards moving gas. The gas is introduced into the bottom part of the reactor. The upwards moving gas passes the fluidised bed wherein a part of the gas reacts in the presence of the catalyst and the unreacted gas is withdrawn from the top of the reactor. The gas is then compressed and cooled to remove the heat of
- Fluidised bed polymerisation reactors are disclosed, among others, in US-A-4994534, US-A-4588790, EP-A-699213, EP-A-628343, FI-A-921632, FI-A-935856, US-A-4877587, FI-A-933073 and EP-A-75049.
- the polymer is suitably transferred from the second polymerisation step into the third polymerisation step as described in EP-A-1415999.
- the procedure described in paragraphs [0037] to [0048] of EP-A-1415999 provides an economical and effective method for product transfer.
- the conditions in the third polymerisation step are adjusted so that the resulting second ethylene polymer mixture (PEM2) has MFRs of from 0.1 to 5 g/10 min, preferably > 0.1 to 2 g/10 min, preferably 0.2 to 1 g/10min, further preferred 0.3 to ⁇ 0.8 g/10 min.
- the second ethylene polymer mixture has a density in the range of 920 to 940 kg/m 3 , 925 to 936 kg/m 3 , preferably 926 to 935 kg/m 3 .
- the polymerisation rate in the third polymerisation step is suitably controlled to achieve the desired amount of the third ethylene copolymer in the second ethylene polymer mixture.
- the second ethylene polymer mixture contains from 45 to 65 % by weight, preferably 50 to 62 % by weight, further preferred > 50 to 60 % by weight by weight of the third ethylene copolymer.
- the polymerisation rate is suitably controlled by adjusting the ethylene
- the mole fraction of ethylene in the reactor gas is suitably from 3 to 50 % by mole and preferably from 5 to 15 % by mole.
- the gas also comprises an inert gas.
- the inert gas can be any gas which is inert in the reaction conditions, such as a saturated hydrocarbon having from 1 to 5 carbon atoms, nitrogen or a mixture of the above-mentioned compounds. Suitable hydrocarbons having from 1 to 5 carbon atoms are methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and mixtures thereof.
- process steps for removing residual hydrocarbons from the polymer are well known in the art and can include pressure reduction steps, purging steps, stripping steps, extraction steps and so on. Also combinations of different steps are possible.
- a part of the hydrocarbons is removed from the polymer powder by reducing the pressure.
- the powder is then contacted with steam at a temperature of from 90 to 110 °C for a period of from 10 minutes to 3 hours. Thereafter the powder is purged with inert gas, such as nitrogen, over a period of from 1 to 60 minutes at a temperature of from 20 to 80 °C.
- the polymer powder is subjected to a pressure reduction as described above. Thereafter it is purged with an inert gas, such as nitrogen, over a period of from 20 minutes to 5 hours at a temperature of from 50 to 90 °C.
- the inert gas may contain from 0.0001 to 5 %, preferably from 0.001 to 1 %, by weight of components for deactivating the catalyst contained in the polymer, such as steam.
- the purging steps are preferably conducted continuously in a settled moving bed.
- the polymer moves downwards as a plug flow and the purge gas, which is introduced to the bottom of the bed, flows upwards.
- Suitable processes for removing hydrocarbons from polymer are disclosed in WO-A-02/088194, EP-A-683176, EP-A-372239, EP-A-47077 and GB-A-1272778.
- the polymer is preferably mixed with additives as it is well known in the art.
- additives include antioxidants, process stabilisers, neutralisers, lubricating agents, nucleating agents, pigments and so on.
- the polymer particles are mixed with additives and extruded to pellets as it is known in the art.
- a counter-rotating twin screw extruder is used for the extrusion step.
- Such extruders are manufactured, for instance, by Kobe and Japan Steel Works.
- a suitable example of such extruders is disclosed in EP-A-1600276.
- SEI specific energy input
- the melt temperature is typically from 220 to 290 °C.
- the a-olefin comonomer may be selected from the group consisting of a-olefins having from 4 to 10 carbon atoms and their mixtures, preferably from the group consisting of a-olefins having from 4 to 8 carbon atoms and their mixtures, further preferred from the group consisting of 1 -butene, 1 -hexene and 1-octene, further preferred wherein only ethylene is polymerized in the first and second polymerization steps and two comonomers are used in the third polymerization step, whereby the a-olefin comonomers in the third polymerization step are 1 -butene and 1 -hexene.
- the third polymerisation step is conducted in gas phase, preferably in a gas phase fluidized bed reactor, further preferred connected in series.
- At least one of the first and the second polymerisation step(s) is/are conducted as a slurry polymerisation in a loop reactor, preferably both the first and the second polymerisation steps are conducted as a slurry polymerisation in two loop reactors, preferably connected in series.
- the diluent in the slurry in an embodiment of the process according to the invention, the diluent in the slurry
- polymerisation may comprises at least 90 % of hydrocarbons having from 3 to 5 carbon atoms.
- the second ethylene polymer mixture may comprise from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to ⁇ 25 % by weight of the first ethylene homo- or copolymer, from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to ⁇ 25 % by weight of the second ethylene homo- or copolymer and from 45 to 65 % by weight, preferably 50 to 62 % by weight, further preferred > 50 to 60 % by weight of the third ethylene copolymer.
- the second ethylene polymer mixture may have a density of from 925 to 936 kg/m 3 , preferably 926 to 935 kg/m 3 , and/or a melt flow rate MFRs of from > 0.1 to 2 g/10 min, preferably 0.2 to 1 g/10min, further preferred 0.3 to ⁇ 0.8 g/10 min.
- the second ethylene polymer mixture may have a density of from 927 to 936 kg/m 3 , preferably 926 to 935 kg/m 3
- the first ethylene homo- or copolymer (PE1) may have a density of from 940 to 980 kg/m 3 and/or a melt flow rate MFR2 of from 20 to 280 g/10 min
- the first ethylene polymer mixture (PEM1) may have a density of from 940 to 980 kg/m 3 and a melt flow rate MFR2 of from 150 to 550 g/10 min.
- the ratio MFR 2 (PEM1) / MFR 2 (PE1) may be between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
- the present invention also concerns a multimodal ethylene polymer film composition having density of from 920 to 940 kg/m 3 and/or a melt flow rate MFR5 of from 0.1 to 5 g/10 min and produced according to any of claim 1 to 1 0.
- a multimodal ethylene- alpha-olefin copolymer film composition according to the invention may have density of from 920 to 940 kg/m 3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min and comprising a first ethylene homo- or copolymer (PE1), a second ethylene homo- or copolymer (PE2) and a third ethylene copolymer (PE3), wherein the first ethylene homo- or copolymer (PE1) and the second ethylene homo- or copolymer (PE2) form a first ethylene polymer mixture (PEM1) and the first ethylene polymer mixture (PEM1) and the third ethylene copolymer (PE3) form the second ethylene polymer mixture (PEM2), and wherein
- the first ethylene homo- or copolymer (PE1) has a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m 3 ;
- the first ethylene polymer mixture (PEM1) has a melt flow rate MFR2 of from 100 to
- the second ethylene polymer mixture has a density of from 920 to 940 kg/m 3 and a melt flow rate MFRs of from 0.1 to 5 g/10 min.
- MFR 2 (PEM1) / MFR 2 (PE1) may be between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
- the multimodal film composition of the present invention is produced in at least three polymerisation steps, and may be a trimodal polyethylene composition.
- the film according to the present invention comprises the multimodal ethylene copolymer film composition, preferably a trimodal polyethylene film composition.
- the film composition may also contain antioxidants, process stabilizers, slip agents, pigments, UV-stabilizers and other additives known in the art.
- stabilizers are hindered phenols, hindered amines, phosphates, phosphites and phosphonites.
- pigments are carbon black, ultramarine blue and titanium dioxide.
- other additives are e. g. clay, talc, calcium carbonate, calcium stearate, zinc stearate and antistatic additives like.
- the additives can be added as single components or as part of a masterbatch as is known in the art.
- Suitable antioxidants and stabilizers are, for instance, 2,6-di-tert-butyl-p-cresol, tetrakis- [methylene-3-(3’,5-di-tert-butyl-4’hydroxyphenyl)propionate]methane, octadecyl-3-3(3’5’-di-tert- butyl-4’-hydroxyphenyl)propionate, dilaurylthiodipropionate, distearylthiodipropionate, tris- (nonylphenyl)phosphate, distearyl-pentaerythritol-diphosphite and tetrakis(2,4-di-tert- butylphenyl)-4,4’-biphenylene-diphosphonite.
- Some hindered phenols are sold under the trade names of Irganox 1076 and Irganox 1010 or commercially available blends thereof, like Irganox B561.
- Commercially available blends of antioxidants and process stabilizers are also available, such as Irganox B225 marketed by Ciba-Geigy.
- Suitable acid scavengers are, for instance, metal stearates, such as calcium stearate and zinc stearate. They are used in amounts generally known in the art, typically from 300 ppm to 10000 ppm and preferably from 400 to 5000 ppm.
- the polymer of the invention can be provided in the form of powder or pellets, preferably pellets. Pellets are obtained by conventional extrusion, granulation or grinding techniques and are an ideal form of the polymer of the invention because they can be added directly to converting machinery. Pellets are distinguished from polymer powders where particle sizes are less than 1 mm. The use of pellets ensures that the composition of the invention is capable of being converted in a film, e.g. monolayer film, by the simple in line addition of the pellets to the converting machinery.
- the multimodal ethylene polymer film compositions of the invention allow the formation of films having good mechanical properties.
- the composition can be extruded to films according to any method known in the art.
- the film preparation process steps of the invention are known and may be carried out in a film line in a manner known in the art, such as flat film extrusion or blown film extrusion.
- Well known film lines are commercially available, for example from
- the ethylene polymer compositions of the invention have extraordinary processing properties. Multimodality, especially trimodality, of the polyethylene film composition of the invention makes it very beneficial for making films. Benefits can be seen in excellent
- the maximum output of the film composition of the invention with 40 pm film is at least 15 % higher, preferably at least 20 % higher, more preferably at least 25 % higher, even more than 30 % higher than with commercial film composition having corresponding MFR and density as composition of the invention.
- the multimodal film composition of the invention is very attractive in film making point of view.
- the films of the invention are preferably monolayer films or the polymer composition of the invention is used to form a layer within a multilayer film.
- Any film of the invention may have a thickness of 3 to 1000 pm, preferably 5 to 500 pm, more preferably 10 to 250 pm, still more preferably 10 to 150 pm, such as e.g. 10 to 100 pm, or even 10 to 60 pm. Selected thickness is dependent on the needs of the desired end application.
- compositions produced according to the process of the present invention are suitable for making blown films.
- the films of the invention can be manufactured using simple in line addition of the polymer pellets to an extruder.
- it is especially preferred to thoroughly blend the components for example using a twin screw extruder, preferably a counter- rotating extruder prior to extrusion and film blowing.
- the film of the invention is a blown film. Blown films are typically produced by extrusion through an annular die, blowing into a tubular film by forming a bubble which is collapsed between nip rollers after solidification. This film can then be slit, cut or converted (e.g. gusseted) as desired. Conventional film production techniques may be used in this regard.
- the composition will be extruded at a temperature in the range 160°C to 240°C, and cooled by blowing gas (generally air) at a temperature of 10 to 50°C to provide a frost line height of 1 or 2 to 8 times the diameter of the die.
- blowing gas generally air
- the blow up ratio (BUR) should generally be in the range 1.5 to 4, e.g. 2 to 4, preferably 2.5 to 3.
- the films of the invention exhibit high dart impact strengths and tear strengths, especially in the machine direction.
- certain parameters are given based on a specific film thickness. This is because variations in thickness of the film cause a change to the size of the parameter in question so to obtain a quantitative value, a specific film thickness is quoted. This does not mean that the invention does not cover other film thicknesses rather it means that when formulated at a given thickness, the film should have the given parameter value.
- Impact resistance on film (ASTM D1709, method“A”) may be between 280 g and 500 g, further preferred between 300 g and 400 g and/or have a tensile modulus between 300 and 490 MPa, preferably 400 and 480 MPa in MD (ISO 527-3).
- the present invention further concerns a process for producing a film, comprising the steps of
- the a-olefin comonomer may be selected from the group consisting of a-olefins having from 4 to 10 carbon atoms and their mixtures, preferably from the group consisting of a-olefins having from 4 to 8 carbon atoms and their mixtures, further preferred from the group consisting of 1 -butene, 1- hexene and 1-octene, further preferred wherein the a-olefin comonomer in the first and second polymerization steps is 1- butene and the a-olefin comonomer in the third polymerization step is 1 -butene and 1 -hexene.
- the invention also concerns a film comprising the multimodal film composition according to the invention.
- the melt flow rate is determined according to ISO 1133 and is indicated in g/10 min.
- the MFR is an indication of the melt viscosity of the polymer.
- the MFR is determined at 190°C for PE.
- the load under which the melt flow rate is determined is usually indicated as a subscript, for instance MFR 2 is measured under 2.16 kg load, MFR 5 is measured under 5 kg load and MFR 21 is measured under 21.6 kg load.
- MFR values can be determined on samples as explained above or calculated, for example in a way well known in the art, from MFR values determined on samples as explained above, especially for example an MFR value for the second ethylene homo- or copolymer can be calculated based on a measured MFR value for the first ethylene homo- or copolymer, a measured MFR value for the first ethylene polymer mixture and the respective amounts of the first and second ethylene homo- or copolymers, since the MFR of the first ethylene polymer mixture results from the first and second ethylene homo- or copolymers.
- Density of the polymer was measured according to ISO 1183-2 / 1872-2B.
- Co-monomer content can be determined according to any suitable method well known in the art to do so, such as for example NMR.
- Film thickness can be determined according to any suitable method well known in the art to do so, such as for example any suitable measuring device.
- the tear strength or tear resistance is measured using the ISO 6383/2 method.
- the force required to propagate tearing across a film specimen is measured using a pendulum device.
- the pendulum swings under gravity through an arc, tearing the specimen from a pre-cut slit.
- the specimen is fixed on one side by the pendulum and on the other side by a stationary clamp.
- the tear strength or tear resistance is the force required to tear the specimen.
- the relative tear resistance (N/mm) can be calculated by dividing the tear resistance by the thickness of the film.
- the films were produced as described below in the film preparation example.
- the tear strength or tear resistance is measured in machine direction (MD) and/or transverse direction (TD).
- E-Mod Tensile modulus
- Rheological parameters such as Shear Thinning Index SHI and Viscosity were determined by using a Anton Paar Phisica MCR 300 Rheometer on compression moulded samples under nitrogen atmosphere at 190 °C using 25 mm diameter plates and plate and plate geometry with a 1.2 mm gap.
- the oscillatory shear experiments were done within the linear viscosity range of strain at frequencies from 0.05 to 300 rad/s (ISO 6721-1). Five measurement points per decade were made.
- Shear thinning index (SHI) which correlates with MWD and is independent of Mw, was calculated according to Heino (“Rheological characterization of polyethylene fractions” Heino, E.L., Lehtinen, A., Tanner J., Seppala, J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1 , 360-362, and“The influence of molecular structure on some rheological properties of polyethylene”, Heino, E.L., Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995).
- SHI value is obtained by calculating the complex viscosities at given values of complex modulus and calculating the ratio of the two viscosities. For example, using the values of complex modulus of 5 kPa and 300 kPa, then h*(5 kPa) and h*(300 kPa) are obtained at a constant value of complex modulus of 5 kPa and 300 kPa, respectively.
- the shear thinning index SHI5/300 is then defined as the ratio of the two viscosities h*(5 kPa) and h*(300 kPa), i.e. h(5)/h(300).
- the films were prepared as described below in the film preparation method A.
- a loop reactor having a volume of 50 dm 3 was operated at a temperature of 70 °C and a pressure of 57 bar.
- ethylene, 1-butene, propane diluent and hydrogen so that the feed rate of ethylene was 2.0 kg/h, of 1-butene 99 g/h, of hydrogen was 5 g/h and of propane was 50 kg/h.
- a solid polymerization catalyst component produced as described above and in Example 1 of EP 1378528 was introduced into the reactor together with triethylaluminium cocatalyst so that the molar ratio of Al/Ti was about 15.
- the estimated production rate was for example about 1.3 kg/h.
- a stream of slurry was continuously withdrawn and directed to a loop reactor having a volume of 150 dm 3 and which was operated at a temperature of 95 °C and a pressure of 55 bar.
- Into the reactor were further fed additional ethylene, propane diluent and hydrogen so that the ethylene concentration in the fluid mixture was 3.7% for IE1 , 4.4% for IE2 and 3.6% for IE3 % by mole, the hydrogen to ethylene ratio was 134 mol/kmol for IE1 , 157.9 mol/kmol for IE2 and 267.2 mol/kmol for IE3 and the fresh propane feed was 78-79 kg/h for all three lEs.
- the production rate was for example about 14 kg/h.
- the resulting copolymer had MFR2 of 26 g/10min for IE1 , 57 g/10min for IE2 and 195 g/10min for IE3 and density of for example about 968 kg/m 3 for all three lEs.
- a stream of slurry from the reactor was withdrawn intermittently and directed into a loop reactor having a volume of 350 dm 3 and which was operated at 95 °C temperature and 52-53 bar pressure.
- Into the reactor was further added a fresh propane, ethylene, and hydrogen so that the ethylene content in the reaction mixture was 3.1-3.3 mol-% and the molar ratio of hydrogen to ethylene was 465.9 mol/kmol for IE1 , 436.5 mol/kmol for IE2 and 487.2 mol/kmol for IE3 and the molar ratio of 1-butene to ethylene was 21-22 mol/kmol for all three lEs.
- the ethylene copolymer withdrawn from the reactor had MFR2 of 200 g/10min for IE1 , 197 g/10min for IE2 and 468 g/10min for IE3 and density of for example about 968 kg/m 3 for all three lEs
- the production rate was for example about 24 kg/h.
- the slurry was withdrawn from the loop reactor intermittently and directed to a flash vessel operated at a temperature of 50 °C and a pressure of 3 bar. From there the polymer was directed to a fluidized bed gas phase reactor operated at a pressure of 20 bar and a
- the polymer had a melt flow rate MFRs of 0.69 g/10 min for IE1 , 0.78 g/10min for IE2 and 0,79 g/10min for IE3 and a density of 931.0 kg/m 3 for IE1 , 931.4 kg/m 3 for both IE2 and IE3
- the production split (weight-% prepolymer/weight-% 1st step component/weight-% 2nd step component/weight-% 3rd step component) was about 1/19 /22 /58 .
- the polymer powder was mixed under nitrogen atmosphere with 1200 ppm of Irganox B561 and 400 ppm Ca-stearate. Then it was compounded and extruded under nitrogen atmosphere to pellets by using a JSW CIMP90 twin screw extruder so that the SEI was 155 kWh/ton for IE1 , 163-164 kWh/ton for IE2 and IE3 and the melt temperature of 250 °C.
- the pelletised resin had a melt flow rate MFRs of 0.64 g/10 min for IE1 , 0.78 g/10min for IE2 and 0.71 g/10min for IE3, a density of 930 kg/for IE1 and 932 kg/m 3 for both IE2 and IE3. They have the SHI (5/300) of 93.1 for IE1 , 74.6 for IE2 and 99.2 for IE3.
- Blown films were made in 7-layer Alpine line under the following conditions: Extruder temperature settings were for all extruders: 220-230-230-230-230-235-235 in all test points. Further the following parameters were used: Blow Up Ratio (BUR) of 3.0; frost line height of 850 0mm, which is about 3 times of die diameter (300mm); and die gap of 1 ,5mm. Layered structure of the monolayer film produced from 7-layer Alpine line of 14/14/14/14/14/15/15.
- BUR Blow Up Ratio
- BUR Blow Up Ratio
- BUR indicates the increase in the bubble diameter over the die diameter.
- a blow-up ratio greater than 1 indicates that the bubble has been blown to a diameter greater than that of the die orifice.
- Maximum output rate (kg/h) was tested for materials at 40 micron film thickness.
- the blown film is wound to form reels which are followed by film cutting into respective dimension for further mechanical testing.
Abstract
The present invention deals with a process for producing a multimodal ethylene polymer composition suitable for producing films by blow moulding. The process comprises (i) (co)polymerising ethylene and optionally an alpha-olefin comonomer in a first polymerisation step in the presence of a silica supported Ziegler-Natta polymerisation catalyst to produce a first ethylene homo- or copolymer (PE1) having a melt flow rate MFR2 of from 15 to 300 g/10 min; (ii) (co)polymerising ethylene and optionally an alpha-olefin comonomer in a second polymerisation step in the presence of the first ethylene homo- or copolymer to produce a first ethylene polymer mixture (PEM1) comprising the first ethylene homo- or copolymer and a second ethylene copolymer, said first ethylene polymer mixture having a density of from 940 to 980 kg/m3 and a melt flow rate MFR2 of from 100 to 600 g/10 min, and wherein the MFR2 of the first ethylene homo- or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1) and the second ethylene homo- or copolymer (PE2) has a melt flow rate MFR2 of from 400 to 2000 g/10min and (iii) copolymerising ethylene and at least one alpha-olefin comonomer in a third polymerisation step in the presence of the first ethylene polymer mixture to produce a second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture and a third ethylene copolymer (PE3), said second ethylene polymer mixture having a density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min.
Description
A process for producing polyolefin film composition and films prepared thereof
Field of the Invention
The present invention is directed to a method for producing multimodal ethylene polymer film compositions and films prepared thereof. Especially, the present invention is directed to a method for making multimodal ethylene copolymer film composition by a process comprising polymerizing ethylene in at least three polymerization stages. Further, the present invention is directed to films comprising the multimodal ethylene copolymer composition produced by the method comprising at least three polymerization stages. Further, the invention is directed to the use of such multimodal ethylene copolymer compositions for making films with improved processability and throughput.
Related Art and Problem to Be Solved
It is known to produce ethylene copolymers suitable for producing films by copolymerizing ethylene in two polymerization stages, for instance from EP-A-691367 which discloses bimodal ethylene copolymers produced in two fluidized bed reactors.
Also WO-A-2004000902 discloses bimodal low density PE resins. The document does not disclose multimodal ethylene polymer composition produced in three polymerisation stage.
EP-A-2067799 discloses multimodal LLDPE resins which have been produced in two polymerization stages in a loop and a gas phase reactor in the presence of a ligand-modified catalyst. The document does not disclose a third polymerization stage.
EP-A-2246369 discloses LLDPE produced in the presence of a Ziegler-Natta catalyst with specific halogenated aluminium alkyl compounds as a cocatalyst. While the document briefly refers to two-stage polymerization its examples are one-stage polymerization runs. The document does not disclose any three-stage polymerization.
EP-A-2246372 discloses LLDPE produced in the presence of a Ziegler-Natta catalyst with a halogenated aluminium alkyl compounds as a cocatalyst. The document discloses ethylene copolymerisation in two-stage polymerization configuration. It’s only generally mentioned that optionally additional reactors may be used. It does not, however, disclose the nature of the polymers produced in such stages and it exemplifies only two-stage polymerization.
EP-A-2228394 discloses LLDPE polymers produced in two polymerization stages using amulticomponent catalyst comprising titanium and vanadium compounds. The document discloses that it is possible to include further polymerization stages, such as a third and a fourth polymerization stage which are preferably conducted in gas phase. It does not, however, disclose the nature of the polymers produced in such stages and it exemplifies only two-stage polymerization.
EP-A-2186833 discloses a three-stage polymerization in a cascaded reactor sequence of two loop reactors followed by a gas phase reactor. In the first stage a polymer having an M FR2 of preferably 200 to 1000 g/10 min and a density of preferably 945 to 978 kg/m3 is produced. The polymer produced in the second stage is disclosed to have an MFR2 of preferably 200 to 1000 g/10 min and a density of preferably 945 to 978 kg/m3. The final polymer had an MFR21 of preferably 5 to 30 g/10 min and a density of preferably 940 to 970 kg/m3. The polymers produced in the first and second stages had the same MFR2. In the exemplified process the polymers produced in the first two stages were homopolymers and the final resins had MFR5 of from 0.2 to 0.4 g/10 min and density of about 955 kg/m3.
EP2415598 discloses a multilayer film comprising at least one layer of a multimodal terpolymer, e.g. a bimodal linear low density ethylene/1 -butene/C6-Ci2-alpha-olefin terpolymer. The multimodal polymer comprises a low molecular weight component corresponding ethylene homopolymer or a low molecular weight ethylene copolymer and a high molecular weight component corresponding to ethylene terpolymer with higher alpha-olefin comonomers.
Preferably the low molecular weight component is an ethylene homoplymer and the high molecular weight component is ethylene/1 -butene/1 -hexene terpolymer. The multimodal terpolymer is produced in a two stage polymerisation process. Final densities are disclosed to be in the range of 910 - 950 kg/m3 or 935 - 970 kg/m3 or 900 - 935 kg/m3; and MFR21 (190 °C, 21 ,6 kg load, IS01133) 7 to 60 g/10min or 2 to 35 g/10min or 15 to 80 g/10min, respectively.
WO 2015/086812 (EP2883887) describes a process for making multimodal ethylene copolymers where the method comprises polymerising ethylene and comonomers in three polymerisation stages, and further use of said copolymers for making films. The ethylene copolymer produced according to the process has the density of 906 to 925 kg/m3 and MFR5 (190 °C, 5,0 kg load, IS01133) of 0,5 to 5,0 g/10 min. The copolymer produced in the first polymerisation stage and the first copolymer mixture being a mixture of the first polymer and polymer produced in the second stage have claimed densities in the range of 945 to 955 kg/m3 and melt flow rates MFR2 in the range of 150 to 1000 kg/m3.
EP2883885 describes similar type of polymers as described in WO 2015/086812.
Many unimodal or bimodal ethylene polymers have desired properties for different application needs. Suitable densities and melt flow rates are normal decisive features of polyethylene film materials. Such bimodal terpolymers are known in the state of the art and are described e.g. in WO 03/066698 or WO 2008/034630 or are commercially available, such as BorShape™ FX1001 and BorShape™ FX1002 (both from Borealis AG, Vienna, Austria).
Even though the basic properties (density, melt flow ratio and mechanical properties) of polyethylene composition for making films might be satisfactory with known polyethylene film compositions, there still remains a need to provide a polyethylene film composition having in addition improved throughput (output) and/or extrudability properties in film making processes. High throughput and/or excellent extrudability properties are very much appreciated by the film makers. Combinations of desired properties, especially mechanical properties, such as for example DDI and/or tear, of polymer film composition and/or good processability with high throughput in film making process are mostly not discussed in related art publications.
The present invention therefore provides especially for example good mechanical properties, such as for example DDI and/or tear, of polymer film composition and/or good processability and/or high throughput in a film making process.
Summary of the Invention
The present invention concerns a process for producing multimodal ethylene polymer film compositions comprising the steps of
(i) (co)polymerising ethylene and optionally an alpha-olefin comonomer in a first polymerisation step in the presence of a silica supported Ziegler-Natta polymerisation catalyst to produce a first ethylene homo- or copolymer (PE1) having a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m3;
(ii) (co)polymerising ethylene and optionally an alpha-olefin comonomer in a second
polymerisation step in the presence of the first ethylene homo- or copolymer to produce a first ethylene polymer mixture (PEM1) comprising the first ethylene homo- or copolymer and a second ethylene copolymer, said first ethylene polymer mixture having a density of from 940 to 980 kg/m3 and a melt flow rate MFR2 of from 100 to 600 g/10 min, and wherein the MFR2 0f the first ethylene homo- or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1) and
the second ethylene homo- or copolymer (PE2) has a melt flow rate MFR2 of from 400 to 2000 g/10min and optionally a density of from 940 to 980 kg/m3; and
(iii) copolymerising ethylene and at least one alpha-olefin comonomer in a third polymerisation step in the presence of the first ethylene polymer mixture to produce a second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture and a third ethylene copolymer (PE3), said second ethylene polymer mixture having a density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min.
Detailed description
Polymerisation process
The present process for producing polyethylene film composition comprises polymerisation of ethylene and at least one a-olefin in multiple polymerisation steps in the presence of a polymerisation catalyst. In the present application definition multiple polymerisation steps mean a process comprising at least three polymerisation steps.
The at least one a-olefin one alpha-olefin comonomer may be selected from a-olefins having from 4 to 10 carbon atoms and their mixtures. Especially suitable a-olefins are those having from 4 to 8 carbon atoms, including their mixtures. In particular 1-butene, 1-hexene and 1- octene and their mixtures are the preferred a-olefins. The a-olefin used in the different polymerisation steps may be the same or different.
The polymerisation steps may be connected in any order, i.e. the first polymerisation step may precede the second polymerisation step, or the second polymerisation step may precede the first polymerisation step or, alternatively, polymerisation steps may be connected in parallel. However, it is preferred to operate the polymerisation steps in cascaded mode.
Catalyst
The polymerisation is conducted in the presence of an olefin polymerisation catalyst. The catalyst may be any catalyst which is capable of producing all components of the multimodal ethylene copolymer. Suitable catalysts are, among others, Ziegler - Natta catalysts based on a transition metal, such as titanium, zirconium and/or vanadium or metallocene catalysts or late transition metal catalysts, as well as their mixtures. Especially Ziegler - Natta catalysts are
useful as they can produce polymers within a wide range of molecular weight and other desired properties with a high productivity. Ziegler - Natta catalysts used in the present invention are supported on an external support.
Suitable Ziegler - Natta catalysts preferably contain a magnesium compound, an aluminium compound and a titanium compound supported on a particulate support.
The particulate support typically used in Ziegler-Natta catalysts comprises an inorganic oxide support, such as silica, alumina, titania, silica-alumina and silica-titania or a MgCh based support. The catalyst used in the present invention is supported on an inorganic oxide support. Most preferably the Ziegler-Natta catalyst used in the present invention is supported on silica.
The average particle size of the silica support can be typically from 10 to 100 mhi. However, it has turned out that special advantages can be obtained if the support has an average particle size from 15 to 30 mhi, preferably from 18 to 25 mhi. Alternatively, the support may have an average particle size of from 30 a 80 mhi, preferably from 30 to 50 mhi. Examples of suitable support materials are, for instance, ES747JR produced and marketed by Ineos Silicas (former Crossfield), and SP9-491 , produced and marketed by Grace.
The magnesium compound is a reaction product of a magnesium dialkyl and an alcohol. The alcohol is a linear or branched aliphatic monoalcohol. Preferably, the alcohol has from 6 to 16 carbon atoms. Branched alcohols are especially preferred, and 2-ethyl-1-hexanol is one example of the preferred alcohols. The magnesium dialkyl may be any compound of magnesium bonding to two alkyl groups, which may be the same or different. Butyl-octyl magnesium is one example of the preferred magnesium dialkyls.
The aluminium compound is chlorine containing aluminium alkyl. Especially preferred compounds are aluminium alkyl dichlorides, aluminium dialkyl chlorides and aluminium alkyl sesquichlorides.
The transition metal is preferably titanium. The titanium compound is a halogen containing titanium compound, preferably chlorine containing titanium compound. Especially preferred titanium compound is titanium tetrachloride.
The catalyst can be prepared by sequentially contacting the carrier with the above mentioned compounds, as described in EP-A-688794 or WO-A-99/51646. Alternatively, it can be prepared
by first preparing a solution from the components and then contacting the solution with a carrier, as described in WO-A-01/55230.
The Ziegler - Natta catalyst is used together with an activator, which is also called as cocatalyst. Suitable activators are metal alkyl compounds, typically Group 13 metal alkyl compounds, and especially aluminium alkyl compounds. They include trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, tri-isobutylaluminium,
trihexylaluminium and tri-n-octylaluminium. Aluminium alkyl compounds may also include alkyl aluminium halides, such as ethylaluminium dichloride, diethylaluminium chloride,
ethylaluminium sesquichloride, dimethylaluminium chloride and the like and alkylaluminium oxy- compounds, such as methylaluminiumoxane, hexaisobutylaluminiumoxane and
tetraisobutylaluminiumoxane and also other aluminium alkyl compounds, such as
isoprenylaluminium. Especially preferred cocatalysts are trialkylaluminiums, of which
triethylaluminium, trimethylaluminium and tri-isobutylaluminium are particularly preferred.
The amount in which the activator is used depends on the specific catalyst and activator.
Typically triethylaluminium is used in such amount that the molar ratio of aluminium to the transition metal, like Al/Ti, is for example from 1 to 1000, preferably from 3 to 100 and in particular from about 5 to about 30 mol/mol.
Prepolymerisation
In addition to the actual polymerisation steps, i.e. in the present invention in addition to the at least three polymerisation steps, the process may comprise a prepolymerisation step preceding the actual polymerisation steps. The purpose of the prepolymerisation is to polymerise a small amount of polymer onto the catalyst at a low temperature and/or a low monomer concentration. By prepolymerisation it is possible to improve the performance of the catalyst in slurry and/or modify the properties of the final polymer. The prepolymerisation step is conducted in slurry.
Thus, the prepolymerisation step may be conducted in a loop reactor. The prepolymerisation is then preferably conducted in an inert diluent, typically a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes etc., or their mixtures. Preferably the diluent is a low-boiling hydrocarbon having from 1 to 4 carbon atoms or a mixture of such hydrocarbons.
The temperature in the prepolymerisation step is typically from 0 to 90 °C, preferably from 20 to 80 °C and more preferably from 55 to 75 °C.
The pressure is not critical and is typically from 1 to 150 bar, preferably from 40 to 80 bar.
The amount of monomer is typically such that from about 0.1 to 1000 grams of monomer per one gram of solid catalyst component is polymerised in the prepolymerisation step. As the person skilled in the art knows, the catalyst particles recovered from a continuous
prepolymerisation reactor do not all contain the same amount of prepolymer. Instead, each particle has its own characteristic amount which depends on the residence time of that particle in the prepolymerisation reactor. As some particles remain in the reactor for a relatively long time and some for a relatively short time, then also the amount of prepolymer on different particles is different and some individual particles may contain an amount of prepolymer which is outside the above limits. However, the average amount of prepolymer on the catalyst typically is within the limits specified above.
The molecular weight of the prepolymer may be controlled by hydrogen as it is known in the art. Further, antistatic additive may be used to prevent the particles from adhering to each other or the walls of the reactor, as disclosed in WO-A-96/19503 and WO-A-96/32420.
The catalyst components are preferably all (separately or together) introduced to the
prepolymerisation step when a prepolymerisation step is present. However, where the solid catalyst component and the cocatalyst can be fed separately it is possible that only a part of the cocatalyst is introduced into the prepolymerisation stage and the remaining part into subsequent polymerisation stages. Also in such cases it is necessary to introduce so much cocatalyst into the prepolymerisation stage that a sufficient polymerisation reaction is obtained therein.
Typically, the amounts of hydrogen and comonomer are adjusted so that the presence of the prepolymer has no effect on the properties of the final multimodal polymer. Especially, it is preferred that melt flow rate of the prepolymer is greater than the melt flow rate of the final polymer but smaller than the melt flow rate of the polymer produced in the first polymerisation stage. It is further preferred that the density of the prepolymer is greater than the density of the final polymer. Suitably the density is approximately the same as or greater than the density of the polymer produced in the first polymerisation stage. Further, typically the amount of the prepolymer is not more than about 5 % by weight of the multimodal polymer comprising the prepolymer.
First Polymerisation Step
The first polymerisation step typically operates at a temperature of from 20 to 150 °C, preferably from 50 to 110 °C and more preferably from 60 to 100 °C. The polymerisation may be conducted in slurry, gas phase or solution. In the first polymerisation step the first homo- or copolymer of ethylene is produced. The first ethylene homo-or copolymer has a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m3.
The catalyst may be transferred into the first polymerisation step by any means known in the art. It is thus possible to suspend the catalyst in a diluent and maintain it as homogeneous slurry. Especially preferred it is to use oil having a viscosity form 20 to 1500 mPa-s as diluent, as disclosed in WO-A-2006/063771. It is also possible to mix the catalyst with a viscous mixture of grease and oil and feed the resultant paste into the first polymerisation step. Further still, it is possible to let the catalyst settle and introduce portions of thus obtained catalyst mud into the first polymerisation step in a manner disclosed, for instance, in EP-A-428054. The first polymerisation step may also be preceded by a prepolymerisation step, in which case the mixture withdrawn from the prepolymerisation step is directed into the first polymerisation step.
Into the first polymerisation step ethylene, the a-olefin, optionally an inert diluent, and optionally hydrogen are introduced. Hydrogen and the a-olefin are introduced in such amounts that the melt flow rate MFR2 and the density of the first ethylene homo-or copolymer are in the desired values.
The a-olefin or the alpha-olefin comonomer (these terms may be used interchangeably herein) is as defined above having from 4 to 10 carbon atoms and their mixtures, and especially suitable a-olefins are those having from 4 to 8 carbon atoms, including their mixtures. In particular 1 -butene, 1 -hexene and 1-octene and their mixtures are the preferred a-olefins.
The polymerisation of the first polymerisation step may be conducted in slurry. Then the polymer particles formed in the polymerisation, together with the catalyst fragmented and dispersed within the particles, are suspended in the fluid hydrocarbon. The slurry is agitated to enable the transfer of reactants from the fluid into the particles.
The polymerisation usually takes place in an inert diluent, typically a hydrocarbon diluent such as methane, ethane, propane, n-butane, isobutane, pentanes, hexanes, heptanes, octanes etc., or their mixtures. Preferably the diluent is a low-boiling hydrocarbon having from 1 to 4 carbon
atoms or a mixture of such hydrocarbons. An especially preferred diluent is propane, possibly containing minor amount of methane, ethane and/or butane.
The ethylene content in the fluid phase of the slurry may be from 1 to about 50 % by mole, preferably from about 1.5 to about 20 % by mole and in particular from about 2 to about 15 % by mole. The benefit of having a high ethylene concentration is that the productivity of the catalyst is increased but the drawback is that more ethylene then needs to be recycled than if the concentration was lower.
The slurry polymerisation may be conducted in any known reactor used for slurry
polymerisation. Such reactors include a continuous stirred tank reactor and a loop reactor. It is especially preferred to conduct the polymerisation in loop reactor. In such reactors the slurry is circulated with a high velocity along a closed pipe by using a circulation pump. Loop reactors are generally known in the art and examples are given, for instance, in US-A-4582816, US-A- 3405109, US-A-3324093, EP-A-479186 and US-A-5391654.
If the first ethylene homo-or copolymer is produced in conditions where the ratio of the a-olefin to ethylene is not more than about 400 mol/kmol, such as not more than 300 mol/kmol, then it is usually advantageous to conduct the slurry polymerisation above the critical temperature and pressure of the fluid mixture. Such operation is described in US-A-5391654.
When the first polymerisation step is conducted as slurry polymerisation the polymerisation in the first polymerisation step is conducted at a temperature within the range of from 50 to 115 °C, preferably from 70 to 110 °C and in particular from 80 to 105 °C. The pressure in the first polymerisation step is then from 1 to 300 bar, preferably from 40 to 100 bar.
The amount of hydrogen is adjusted based on the desired melt flow rate of the first ethylene homo-or copolymer and it depends on the specific catalyst used. For many generally used Ziegler - Natta catalysts the molar ratio of hydrogen to ethylene is for example from 10 to 2000 mol/kmol, preferably from 20 to 1000 mol/kmol and in particular from 40 to 800 mol/kmol.
The amount of the a-olefin is adjusted based on the desired density of the first ethylene homo- or copolymer and it, too, depends on the specific catalyst used. For many generally used Ziegler - Natta catalysts the molar ratio of the a-olefin to ethylene is for example from 100 to 1000 mol/kmol, preferably from 150 to 600 mol/kmol.
The polymerisation of the first polymerisation step may also be conducted in gas phase. A preferable embodiment of gas phase polymerisation reactor is a fluidised bed reactor. There the
polymer particles formed in the polymerisation are suspended in upwards moving gas. The gas is introduced into the bottom part of the reactor. The upwards moving gas passes the fluidised bed wherein a part of the gas reacts in the presence of the catalyst and the unreacted gas is withdrawn from the top of the reactor. The gas is then compressed and cooled to remove the heat of polymerisation. To increase the cooling capacity it is sometimes desired to cool the recycle gas to a temperature where a part of the gas condenses. After cooling the recycle gas is reintroduced into the bottom of the reactor. Fluidised bed polymerisation reactors are disclosed, among others, in US-A-4994534, US-A-4588790, EP-A-699213, EP-A-628343, FI-A-921632, FI-A-935856, US-A-4877587, FI-A-933073 and EP-A-75049.
According to the preferred embodiment of present invention, the polymerisation of the first polymerisation step is conducted in slurry.
Further, suitably the polymerisation is conducted at a temperature exceeding the critical temperature of the fluid mixture and pressure exceeding the critical pressure of the fluid mixture.
According to the invention at least one a-olefin may be present in the first polymerisation step, where the polymer produced in the first step is the first ethylene homo- or copolymer. Typically the density of the first ethylene homo-or copolymer is for example from 940 to 980 kg/m3. The polymerisation is preferably conducted as a slurry polymerisation in liquid diluent at a
temperature of from 75 °C to 100 °C, such as from 80 to 95 °C and a pressure of from 30 bar to 100 bar, such as from 40 to 80 bar, like from 50 to 80 bar. The molar ratio of the a-olefin to ethylene may be for example from 100 to 1000 mol/kmol, and preferably from 150 to 600 mol/kmol.
The polymerisation rate in the first polymerisation step is suitably controlled to achieve the desired amount of the first ethylene homo-or copolymer in the second ethylene polymer mixture. Preferably the second ethylene polymer mixture contains from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to < 25 % by weight of the first ethylene homo- or copolymer. The polymerisation rate is suitably controlled by adjusting the ethylene
concentration in the first polymerisation step. When the first polymerisation step is conducted as slurry polymerisation in the loop reactor the mole fraction of ethylene in the reaction mixture is suitably for example from 0.5 to 10 % by mole and preferably from 1 to 8 % by mole.
The molar ratio of hydrogen to ethylene is suitably from 50 to 350 mol/kmol, preferably from 75 to 325 mol/kmol and in particular from 100 to 300 mol/kmol in the first polymerisation step.
Second Polymerisation Step
The second homo- or copolymer of ethylene is produced in the second polymerisation step in the presence of the first homo- or copolymer of ethylene.
The second polymerisation step typically operates at a temperature of from 20 to 150 °C, preferably from 50 to 110 °C and more preferably from 60 to 100 °C. The polymerisation may be conducted in slurry, gas phase or solution. In the second polymerisation step the second homo- or copolymer of ethylene is produced in the presence of the first homo- or copolymer of ethylene. The first homo- or copolymer of ethylene (PE1) and the second homo- or copolymer of ethylene (PE2) together form the first ethylene polymer mixture (PEM1). The first ethylene polymer mixture has a density of from 940 to 980 kg/m3 and a melt flow rate MFR2 of from 100 to 600 g/10 min.
The first homo- or copolymer of ethylene (PE1) is transferred from the first polymerisation step to the second polymerisation step by using any method known to the person skilled in the art. If the first polymerisation step is conducted as slurry polymerisation in a loop reactor, it is advantageous to transfer the slurry from the first polymerisation step to the second
polymerisation step by means of the pressure difference between the first polymerisation step and the second polymerisation step.
Into the second polymerisation step ethylene, optionally an inert diluent, and optionally hydrogen and/or the a-olefin are introduced. Hydrogen and the a-olefin, are introduced in such amounts that the melt flow rate MFR2 and the density of the first ethylene polymer mixture are within the desired values.
The polymerisation of the second polymerisation step may be conducted in slurry in the same way as it was discussed above for the first polymerisation step.
The amount of hydrogen in the second polymerisation step is adjusted based on the desired melt flow rate of the first ethylene polymer mixture and it depends on the specific catalyst used. For many generally used Ziegler - Natta catalysts the molar ratio of hydrogen to ethylene is for example from 100 to 2000 mol/kmol, preferably from 200 to 1000 mol/kmol and in particular from 250 to 800 mol/kmol.
The amount of the a-olefin is adjusted based on the desired density of the first ethylene polymer mixture and it, too, depends on the specific catalyst used. For many generally used Ziegler -
Natta catalysts the molar ratio of the a-olefin to ethylene is for example from 0 to 1000 mol/kmol, preferably from 0 to 800 mol/kmol and in particular from 0 to 700 mol/kmol.
The polymerisation of the second polymerisation step may also be conducted in gas phase in the same way as was discussed above for the first polymerisation step. Preferably the second polymerisation step is conducted in slurry phase as described above.
It is thus preferred to conduct the second polymerisation step for producing the first ethylene polymer mixture (PEM1) having MFR2 of from 100 to 600 g/10 min , in slurry polymerisation.
The molar ratio of hydrogen to ethylene is suitably from 350 to 600 mol/kmol, preferably from 375 to 550 mol/kmol and in particular from 400 to 500 mol/kmol in the second polymerisation step.
Further, suitably the polymerisation is conducted at a temperature exceeding the critical temperature of the fluid mixture and pressure exceeding the critical pressure of the fluid mixture.
According to the present invention the a-olefin is present in the first polymerisation step and in the second polymerisation step. The density of the first ethylene homo-or copolymer is controlled by the molar ratio of the a-olefin to ethylene in the first polymerisation step and the density of the first ethylene polymer mixture is controlled by the molar ratio of the a-olefin to ethylene in the second polymerisation step. The molar ratio of the a-olefin to ethylene may then be for example from 50 to 1000 mol/kmol, and preferably from 100 to 600 mol/kmol in the second polymerisation step.
The a-olefin used in the second polymerisation step may be the same or different as used in the first polymerisation step.
The polymerisation rate in the second polymerisation step is suitably controlled to achieve the desired amount of the second ethylene homo- or copolymer in the second ethylene polymer mixture. Preferably the second ethylene polymer mixture contains from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to < 25 % by weight of the second ethylene copolymer. The polymerisation rate is suitably controlled by adjusting the ethylene concentration in the second polymerisation step. When the second polymerisation step is conducted as slurry polymerisation in the loop reactor the mole fraction of ethylene in the reaction mixture is suitably from 2 to 10 % by mole and preferably from 3 to 8 % by mole. The mole fraction of ethylene in % by mole in the reaction mixture in the second polymerisation step
may thereby be lower than the mole fraction of ethylene in % by mole in the reaction mixture in the first polymerisation step.
As indicated above the melt flow rate MFR2 0f the first ethylene homo-or copolymer (PE1) is in the range 15 to 300 g/10 min and the melt flow rate MFR2 of the first ethylene homo-or copolymer mixture (PEM1) is in the range 100 to 600 g/10 min and MFR2 (PE1) <
MFR2(PEM1). I.e. the MFR2 0f the polymer produced in the first reactor is lower than the polymer mixture produced in the second polymerisation reactor. According to a preferred embodiment the ratio of MFR2(PEM1)/MFR2 (PE1) may be for example between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
Third Polymerisation Step
In the third polymerisation step the second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture (PEM1) and the third ethylene copolymer (PE3) is formed.
Into the third polymerisation step are introduced ethylene, at least one a-olefin having 4 to 10 carbon atoms, hydrogen and optionally an inert diluent. The polymerisation in third
polymerisation step is conducted at a temperature within the range of from 50 to 100 °C, preferably from 60 to 100 °C and in particular from 70 to 95 °C. The pressure in the third polymerisation step is for example from 1 to 300 bar, preferably from 5 to 100 bar.
The polymerisation in the third polymerisation step may be conducted in slurry. The
polymerisation may then be conducted along the lines as was discussed above for the first and second polymerisation steps.
The amount of hydrogen in the third polymerisation step is adjusted for achieving the desired melt flow rate of the second ethylene polymer mixture. The molar ratio of hydrogen to ethylene depends on the specific catalyst used. For many generally used Ziegler - Natta catalysts the molar ratio of hydrogen to ethylene is for example from 0 to 50 mol/kmol, preferably from 3 to 35 mol/kmol.
Furthermore, the amount of a-olefin having from 4 to 10 carbon atoms is adjusted to reach the targeted density. The ratio of the a-olefin (sum of a-olefins) to ethylene depends on the type of the catalyst and the type of the a-olefin. The ratio is typically for example from 100 to 1000 mol/kmol, preferably from 150 to 800 mol/kmol. If more than one a-olefin is used the ratio of the a-olefin to ethylene is the ratio of the sum of all the a-olefins to ethylene.
The a-olefin used in the third polymerisation step may be the same or different as used in the previous polymerisation steps. The a-olefin is preferably an a-olefin of 4 to 8 carbon atoms or mixtures thereof. In particular 1-butene, 1-hexene and 1-octene and their mixtures are the preferred a-olefins, especially preferred 1 -butene and 1 -hexene.
Alternatively, the polymerisation in the third polymerisation step may be, and preferably is, conducted in gas phase. In gas phase polymerisation using a Ziegler - Natta catalyst hydrogen is typically added in such amount that the ratio of hydrogen to ethylene is for example from 3 to 100 mol/kmol, preferably from 4 to 50 mol/kmol for obtaining the desired melt index of the second ethylene polymer mixture. The amount of a-olefin having from 4 to 10 carbon atoms is adjusted to reach the targeted density of the second ethylene polymer mixture. The ratio of the a-olefin to ethylene is typically from 100 to 1000 mol/kmol, preferably from 150 to 800 mol/kmol, further preferred < 150 to 300 mol/kmol. If more than one a-olefin is used the ratio of the a-olefin to ethylene is the ratio of the sum of all the a-olefins to ethylene.
The gas phase reactor preferably is a vertical fluidised bed reactor. There the polymer particles formed in the polymerisation are suspended in upwards moving gas. The gas is introduced into the bottom part of the reactor. The upwards moving gas passes the fluidised bed wherein a part of the gas reacts in the presence of the catalyst and the unreacted gas is withdrawn from the top of the reactor. The gas is then compressed and cooled to remove the heat of
polymerisation. To increase the cooling capacity it is sometimes desired to cool the recycle gas to a temperature where a part of the gas condenses. After cooling the recycle gas is
reintroduced into the bottom of the reactor. Fluidised bed polymerisation reactors are disclosed, among others, in US-A-4994534, US-A-4588790, EP-A-699213, EP-A-628343, FI-A-921632, FI-A-935856, US-A-4877587, FI-A-933073 and EP-A-75049.
When the second polymerisation step is conducted in slurry and the third polymerisation step is conducted in gas phase, the polymer is suitably transferred from the second polymerisation step into the third polymerisation step as described in EP-A-1415999. The procedure described in paragraphs [0037] to [0048] of EP-A-1415999 provides an economical and effective method for product transfer.
The conditions in the third polymerisation step are adjusted so that the resulting second ethylene polymer mixture (PEM2) has MFRs of from 0.1 to 5 g/10 min, preferably > 0.1 to 2 g/10 min, preferably 0.2 to 1 g/10min, further preferred 0.3 to < 0.8 g/10 min. Furthermore, the second ethylene polymer mixture has a density in the range of 920 to 940 kg/m3, 925 to 936 kg/m3, preferably 926 to 935 kg/m3.
The polymerisation rate in the third polymerisation step is suitably controlled to achieve the desired amount of the third ethylene copolymer in the second ethylene polymer mixture.
Preferably the second ethylene polymer mixture contains from 45 to 65 % by weight, preferably 50 to 62 % by weight, further preferred > 50 to 60 % by weight by weight of the third ethylene copolymer. The polymerisation rate is suitably controlled by adjusting the ethylene
concentration in the third polymerisation step. When the third polymerisation step is conducted in gas phase the mole fraction of ethylene in the reactor gas is suitably from 3 to 50 % by mole and preferably from 5 to 15 % by mole.
In addition to ethylene, comonomer and hydrogen the gas also comprises an inert gas. The inert gas can be any gas which is inert in the reaction conditions, such as a saturated hydrocarbon having from 1 to 5 carbon atoms, nitrogen or a mixture of the above-mentioned compounds. Suitable hydrocarbons having from 1 to 5 carbon atoms are methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane and mixtures thereof.
Post Reactor Treatment
When the polymer has been removed from the polymerisation reactor it is subjected to process steps for removing residual hydrocarbons from the polymer. Such processes are well known in the art and can include pressure reduction steps, purging steps, stripping steps, extraction steps and so on. Also combinations of different steps are possible.
According to one preferred process a part of the hydrocarbons is removed from the polymer powder by reducing the pressure. The powder is then contacted with steam at a temperature of from 90 to 110 °C for a period of from 10 minutes to 3 hours. Thereafter the powder is purged with inert gas, such as nitrogen, over a period of from 1 to 60 minutes at a temperature of from 20 to 80 °C.
According to another preferred process the polymer powder is subjected to a pressure reduction as described above. Thereafter it is purged with an inert gas, such as nitrogen, over a period of from 20 minutes to 5 hours at a temperature of from 50 to 90 °C. The inert gas may contain from 0.0001 to 5 %, preferably from 0.001 to 1 %, by weight of components for deactivating the catalyst contained in the polymer, such as steam.
The purging steps are preferably conducted continuously in a settled moving bed. The polymer moves downwards as a plug flow and the purge gas, which is introduced to the bottom of the bed, flows upwards.
Suitable processes for removing hydrocarbons from polymer are disclosed in WO-A-02/088194, EP-A-683176, EP-A-372239, EP-A-47077 and GB-A-1272778.
After the removal of residual hydrocarbons the polymer is preferably mixed with additives as it is well known in the art. Such additives include antioxidants, process stabilisers, neutralisers, lubricating agents, nucleating agents, pigments and so on.
The polymer particles are mixed with additives and extruded to pellets as it is known in the art. Preferably a counter-rotating twin screw extruder is used for the extrusion step. Such extruders are manufactured, for instance, by Kobe and Japan Steel Works. A suitable example of such extruders is disclosed in EP-A-1600276. Typically the specific energy input (SEI) is during the extrusion within the range of from 100 to 230 kWh/ton. The melt temperature is typically from 220 to 290 °C.
Preferred embodiments
In a embodiment of the process according to the invention, the a-olefin comonomer may be selected from the group consisting of a-olefins having from 4 to 10 carbon atoms and their mixtures, preferably from the group consisting of a-olefins having from 4 to 8 carbon atoms and their mixtures, further preferred from the group consisting of 1 -butene, 1 -hexene and 1-octene, further preferred wherein only ethylene is polymerized in the first and second polymerization steps and two comonomers are used in the third polymerization step, whereby the a-olefin comonomers in the third polymerization step are 1 -butene and 1 -hexene.
In an embodiment of the process according to the invention, the third polymerisation step is conducted in gas phase, preferably in a gas phase fluidized bed reactor, further preferred connected in series.
In an embodiment of the process according to the invention, at least one of the first and the second polymerisation step(s) is/are conducted as a slurry polymerisation in a loop reactor, preferably both the first and the second polymerisation steps are conducted as a slurry polymerisation in two loop reactors, preferably connected in series.
In an embodiment of the process according to the invention, the diluent in the slurry
polymerisation may comprises at least 90 % of hydrocarbons having from 3 to 5 carbon atoms.
In an embodiment of the process according to the invention, the second ethylene polymer mixture (PEM2) may comprise from 10 to 35 % by weight, preferably 13 to 26 % by weight,
further preferred > 15 to < 25 % by weight of the first ethylene homo- or copolymer, from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to < 25 % by weight of the second ethylene homo- or copolymer and from 45 to 65 % by weight, preferably 50 to 62 % by weight, further preferred > 50 to 60 % by weight of the third ethylene copolymer.
In an embodiment of the process according to the invention, the second ethylene polymer mixture may have a density of from 925 to 936 kg/m3, preferably 926 to 935 kg/m3, and/or a melt flow rate MFRs of from > 0.1 to 2 g/10 min, preferably 0.2 to 1 g/10min, further preferred 0.3 to < 0.8 g/10 min.
In an embodiment of the process according to the invention, the second ethylene polymer mixture may have a density of from 927 to 936 kg/m3, preferably 926 to 935 kg/m3, the first ethylene homo- or copolymer (PE1) may have a density of from 940 to 980 kg/m3 and/or a melt flow rate MFR2 of from 20 to 280 g/10 min and the first ethylene polymer mixture (PEM1) may have a density of from 940 to 980 kg/m3 and a melt flow rate MFR2 of from 150 to 550 g/10 min.
In an embodiment of the process according to the invention the ratio MFR2(PEM1) / MFR2(PE1) may be between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
The present invention also concerns a multimodal ethylene polymer film composition having density of from 920 to 940 kg/m3 and/or a melt flow rate MFR5 of from 0.1 to 5 g/10 min and produced according to any of claim 1 to 1 0.
In an embodiment of a multimodal ethylene- alpha-olefin copolymer film composition according to the invention may have density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min and comprising a first ethylene homo- or copolymer (PE1), a second ethylene homo- or copolymer (PE2) and a third ethylene copolymer (PE3), wherein the first ethylene homo- or copolymer (PE1) and the second ethylene homo- or copolymer (PE2) form a first ethylene polymer mixture (PEM1) and the first ethylene polymer mixture (PEM1) and the third ethylene copolymer (PE3) form the second ethylene polymer mixture (PEM2), and wherein
I. the first ethylene homo- or copolymer (PE1) has a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m3;
II. the first ethylene polymer mixture (PEM1) has a melt flow rate MFR2 of from 100 to
600 g/10 min and optionally a density of from 940 to 980 kg/m3, wherein the MFR2 0f
the first ethylene homo-or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1);
III. the second ethylene polymer mixture (PEM2) has a density of from 920 to 940 kg/m3 and a melt flow rate MFRs of from 0.1 to 5 g/10 min.
In an embodiment a multimodal film composition according to the invention, the ratio
MFR2(PEM1) / MFR2(PE1) may be between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
As described above the multimodal film composition of the present invention is produced in at least three polymerisation steps, and may be a trimodal polyethylene composition.
Film
The film according to the present invention comprises the multimodal ethylene copolymer film composition, preferably a trimodal polyethylene film composition. In addition to the multimodal, preferably trimodal ethylene copolymer the film composition may also contain antioxidants, process stabilizers, slip agents, pigments, UV-stabilizers and other additives known in the art. Examples of stabilizers are hindered phenols, hindered amines, phosphates, phosphites and phosphonites. Examples of pigments are carbon black, ultramarine blue and titanium dioxide. Examples of other additives are e. g. clay, talc, calcium carbonate, calcium stearate, zinc stearate and antistatic additives like. The additives can be added as single components or as part of a masterbatch as is known in the art.
Suitable antioxidants and stabilizers are, for instance, 2,6-di-tert-butyl-p-cresol, tetrakis- [methylene-3-(3’,5-di-tert-butyl-4’hydroxyphenyl)propionate]methane, octadecyl-3-3(3’5’-di-tert- butyl-4’-hydroxyphenyl)propionate, dilaurylthiodipropionate, distearylthiodipropionate, tris- (nonylphenyl)phosphate, distearyl-pentaerythritol-diphosphite and tetrakis(2,4-di-tert- butylphenyl)-4,4’-biphenylene-diphosphonite.
Some hindered phenols are sold under the trade names of Irganox 1076 and Irganox 1010 or commercially available blends thereof, like Irganox B561. Commercially available blends of antioxidants and process stabilizers are also available, such as Irganox B225 marketed by Ciba-Geigy.
Suitable acid scavengers are, for instance, metal stearates, such as calcium stearate and zinc stearate. They are used in amounts generally known in the art, typically from 300 ppm to 10000 ppm and preferably from 400 to 5000 ppm.
The polymer of the invention can be provided in the form of powder or pellets, preferably pellets. Pellets are obtained by conventional extrusion, granulation or grinding techniques and are an ideal form of the polymer of the invention because they can be added directly to converting machinery. Pellets are distinguished from polymer powders where particle sizes are less than 1 mm. The use of pellets ensures that the composition of the invention is capable of being converted in a film, e.g. monolayer film, by the simple in line addition of the pellets to the converting machinery.
The multimodal ethylene polymer film compositions of the invention allow the formation of films having good mechanical properties. The composition can be extruded to films according to any method known in the art. The film preparation process steps of the invention are known and may be carried out in a film line in a manner known in the art, such as flat film extrusion or blown film extrusion. Well known film lines are commercially available, for example from
Windmoller & Holscher, Reifenhauser, Hosokawa Alpine etc.
Importantly, the ethylene polymer compositions of the invention have extraordinary processing properties. Multimodality, especially trimodality, of the polyethylene film composition of the invention makes it very beneficial for making films. Benefits can be seen in excellent
extrudability and especially in the clearly higher throughput in the film making machinery than corresponding film materials having the same level of density and MFR. The high throughput is not achieved at the expense of good mechanical properties. In the film making process the maximum output of the film composition of the invention with 40 pm film is at least 15 % higher, preferably at least 20 % higher, more preferably at least 25 % higher, even more than 30 % higher than with commercial film composition having corresponding MFR and density as composition of the invention.
Thus, the multimodal film composition of the invention is very attractive in film making point of view.
The films of the invention are preferably monolayer films or the polymer composition of the invention is used to form a layer within a multilayer film. Any film of the invention may have a thickness of 3 to 1000 pm, preferably 5 to 500 pm, more preferably 10 to 250 pm, still more preferably 10 to 150 pm, such as e.g. 10 to 100 pm, or even 10 to 60 pm. Selected thickness is dependent on the needs of the desired end application.
The compositions produced according to the process of the present invention are suitable for making blown films. The films of the invention can be manufactured using simple in line
addition of the polymer pellets to an extruder. For film formation using a polymer mixture it is important that the different polymer components be intimately mixed prior to extrusion and blowing of the film as otherwise there is a risk of inhomogeneity, e.g. gels, appearing in the film. Thus, it is especially preferred to thoroughly blend the components, for example using a twin screw extruder, preferably a counter- rotating extruder prior to extrusion and film blowing.
Sufficient homogeneity can also be obtained by selecting the screw design for the film extruder such that it is designed for good mixing and homogenizing. The film of the invention is a blown film. Blown films are typically produced by extrusion through an annular die, blowing into a tubular film by forming a bubble which is collapsed between nip rollers after solidification. This film can then be slit, cut or converted (e.g. gusseted) as desired. Conventional film production techniques may be used in this regard. Typically the composition will be extruded at a temperature in the range 160°C to 240°C, and cooled by blowing gas (generally air) at a temperature of 10 to 50°C to provide a frost line height of 1 or 2 to 8 times the diameter of the die. The blow up ratio (BUR) should generally be in the range 1.5 to 4, e.g. 2 to 4, preferably 2.5 to 3.
The films of the invention exhibit high dart impact strengths and tear strengths, especially in the machine direction. In the passages which follow, certain parameters are given based on a specific film thickness. This is because variations in thickness of the film cause a change to the size of the parameter in question so to obtain a quantitative value, a specific film thickness is quoted. This does not mean that the invention does not cover other film thicknesses rather it means that when formulated at a given thickness, the film should have the given parameter value.
Thus, for a 40 pm film manufactured as described below and at maximum output, Impact resistance on film (DDI) (ASTM D1709, method“A”) may be between 280 g and 500 g, further preferred between 300 g and 400 g and/or have a tensile modulus between 300 and 490 MPa, preferably 400 and 480 MPa in MD (ISO 527-3).
The present invention further concerns a process for producing a film, comprising the steps of
(i) copolymerising ethylene and an alpha-olefin comonomer in a first polymerisation step in the presence of a silica supported Ziegler-Natta polymerisation catalyst to produce a first ethylene homo- or copolymer (PE1) having a melt flow rate MFR2 of from 15 to 300 g/10 min and optionally a density of from 940 to 980 kg/m3;
(ii) copolymerising ethylene and an alpha-olefin comonomer in a second polymerisation step in the presence of the first ethylene homo- or copolymer to produce a first ethylene polymer mixture (PEM 1) comprising the first ethylene homo- or copolymer and a second ethylene homo- or copolymer, said first ethylene polymer mixture having a melt flow rate MFR2 of from 100 to 600 g/10 min and optionally a density of from 940 to 980 kg/m3, and wherein the MFR2 0f the first ethylene homo- or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1) and
(iii) copolymerising ethylene and an alpha-olefin comonomer in a third polymerisation step in the presence of the first ethylene polymer mixture to produce a second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture and a third ethylene copolymer, said second ethylene polymer mixture having a density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min and iv) pelletizing the second polymer mixture and
v) providing a film by blow moulding.
In an embodiment of the process for producing film according to the invention, the a-olefin comonomer may be selected from the group consisting of a-olefins having from 4 to 10 carbon atoms and their mixtures, preferably from the group consisting of a-olefins having from 4 to 8 carbon atoms and their mixtures, further preferred from the group consisting of 1 -butene, 1- hexene and 1-octene, further preferred wherein the a-olefin comonomer in the first and second polymerization steps is 1- butene and the a-olefin comonomer in the third polymerization step is 1 -butene and 1 -hexene.
The invention also concerns a film comprising the multimodal film composition according to the invention.
Examples
Methods
The following methods were used to measure the properties that are defined generally above and in examples below. Unless otherwise stated, the film samples used for the measurements and definitions were prepared as described under the heading“Film Sample Preparation”.
Melt Index (Ml) or Melt Flow Rate (MFR)
The melt flow rate (MFR) is determined according to ISO 1133 and is indicated in g/10 min. The MFR is an indication of the melt viscosity of the polymer. The MFR is determined at 190°C for PE. The load under which the melt flow rate is determined is usually indicated as a subscript, for instance MFR2 is measured under 2.16 kg load, MFR5 is measured under 5 kg load and MFR21 is measured under 21.6 kg load. MFR values can be determined on samples as explained above or calculated, for example in a way well known in the art, from MFR values determined on samples as explained above, especially for example an MFR value for the second ethylene homo- or copolymer can be calculated based on a measured MFR value for the first ethylene homo- or copolymer, a measured MFR value for the first ethylene polymer mixture and the respective amounts of the first and second ethylene homo- or copolymers, since the MFR of the first ethylene polymer mixture results from the first and second ethylene homo- or copolymers.
Density
Density of the polymer was measured according to ISO 1183-2 / 1872-2B.
Co-monomer content and film thickness
Co-monomer content can be determined according to any suitable method well known in the art to do so, such as for example NMR. Film thickness can be determined according to any suitable method well known in the art to do so, such as for example any suitable measuring device.
Impact resistance on film (DDI)
Impact resistance on film (DDI) was determined by Dart-drop (g/50%). Dart-drop was measured using ASTM D1709, method "A" (Alternative Testing Technique). A dart with a 38 mm diameter hemispherical head was dropped from a height of 0.66 m onto a film clamped over a hole. If the specimen failed, the weight of the dart was reduced and if it did not fail the weight was increased. At least 20 specimens were tested. One weight is used for each set and the weight is increased (or decreased) from set to set by uniform increments. The weight resulting in failure of 50% of the specimens was calculated and reported.
Relative Tear resistance (determined by Elmendorf tear (N/mm))
The tear strength or tear resistance is measured using the ISO 6383/2 method. The force required to propagate tearing across a film specimen is measured using a pendulum device.
The pendulum swings under gravity through an arc, tearing the specimen from a pre-cut slit.
The specimen is fixed on one side by the pendulum and on the other side by a stationary clamp. The tear strength or tear resistance is the force required to tear the specimen. The relative tear resistance (N/mm) can be calculated by dividing the tear resistance by the thickness of the film. The films were produced as described below in the film preparation example. The tear strength or tear resistance is measured in machine direction (MD) and/or transverse direction (TD).
Tensile modulus (E-Mod (MPa) was measured in machine and/or transverse direction according to ISO 527-3 on film samples prepared as described under the Film Sample preparation with film thickness of 40 pm and at a cross head speed of 1 mm/min for the modulus.
Shear Thinning Index (SHI)
Rheological parameters such as Shear Thinning Index SHI and Viscosity were determined by using a Anton Paar Phisica MCR 300 Rheometer on compression moulded samples under nitrogen atmosphere at 190 °C using 25 mm diameter plates and plate and plate geometry with a 1.2 mm gap. The oscillatory shear experiments were done within the linear viscosity range of strain at frequencies from 0.05 to 300 rad/s (ISO 6721-1). Five measurement points per decade were made.
The values of storage modulus (G'), loss modulus (G") complex modulus (G*) and complex viscosity (h*) were obtained as a function of frequency (co). rpoo is used as abbreviation for the complex viscosity at the frequency of 100 rad/s.
Shear thinning index (SHI), which correlates with MWD and is independent of Mw, was calculated according to Heino (“Rheological characterization of polyethylene fractions” Heino, E.L., Lehtinen, A., Tanner J., Seppala, J., Neste Oy, Porvoo, Finland, Theor. Appl. Rheol., Proc. Int. Congr. Rheol, 11th (1992), 1 , 360-362, and“The influence of molecular structure on some rheological properties of polyethylene”, Heino, E.L., Borealis Polymers Oy, Porvoo, Finland, Annual Transactions of the Nordic Rheology Society, 1995).
SHI value is obtained by calculating the complex viscosities at given values of complex modulus and calculating the ratio of the two viscosities. For example, using the values of complex modulus of 5 kPa and 300 kPa, then h*(5 kPa) and h*(300 kPa) are obtained at a constant value of complex modulus of 5 kPa and 300 kPa, respectively. The shear thinning index SHI5/300 is then defined as the ratio of the two viscosities h*(5 kPa) and h*(300 kPa), i.e. h(5)/h(300).
The films were prepared as described below in the film preparation method A.
Inventive Example IE1-IE3
A loop reactor having a volume of 50 dm3 was operated at a temperature of 70 °C and a pressure of 57 bar. Into the reactor were fed ethylene, 1-butene, propane diluent and hydrogen so that the feed rate of ethylene was 2.0 kg/h, of 1-butene 99 g/h, of hydrogen was 5 g/h and of propane was 50 kg/h. Also a solid polymerization catalyst component produced as described above and in Example 1 of EP 1378528 was introduced into the reactor together with triethylaluminium cocatalyst so that the molar ratio of Al/Ti was about 15. The estimated production rate was for example about 1.3 kg/h.
A stream of slurry was continuously withdrawn and directed to a loop reactor having a volume of 150 dm3 and which was operated at a temperature of 95 °C and a pressure of 55 bar. Into the reactor were further fed additional ethylene, propane diluent and hydrogen so that the ethylene concentration in the fluid mixture was 3.7% for IE1 , 4.4% for IE2 and 3.6% for IE3 % by mole, the hydrogen to ethylene ratio was 134 mol/kmol for IE1 , 157.9 mol/kmol for IE2 and 267.2 mol/kmol for IE3 and the fresh propane feed was 78-79 kg/h for all three lEs. The production rate was for example about 14 kg/h. The resulting copolymer had MFR2 of 26 g/10min for IE1 , 57 g/10min for IE2 and 195 g/10min for IE3 and density of for example about 968 kg/m3 for all three lEs.
A stream of slurry from the reactor was withdrawn intermittently and directed into a loop reactor having a volume of 350 dm3 and which was operated at 95 °C temperature and 52-53 bar pressure. Into the reactor was further added a fresh propane, ethylene, and hydrogen so that the ethylene content in the reaction mixture was 3.1-3.3 mol-% and the molar ratio of hydrogen to ethylene was 465.9 mol/kmol for IE1 , 436.5 mol/kmol for IE2 and 487.2 mol/kmol for IE3 and the molar ratio of 1-butene to ethylene was 21-22 mol/kmol for all three lEs. The ethylene copolymer withdrawn from the reactor had MFR2 of 200 g/10min for IE1 , 197 g/10min for IE2
and 468 g/10min for IE3 and density of for example about 968 kg/m3 for all three lEs The production rate was for example about 24 kg/h.
The slurry was withdrawn from the loop reactor intermittently and directed to a flash vessel operated at a temperature of 50 °C and a pressure of 3 bar. From there the polymer was directed to a fluidized bed gas phase reactor operated at a pressure of 20 bar and a
temperature of 80 °C. Additional ethylene, 1-butene and 1-hexene comonomers, nitrogen as inert gas and hydrogen were added so that the ethylene content in the reaction mixture was 9.7 mol-% for IE1 , 9.3 mol% for IE2 and 7.8 mol% for IE3 the ratio of hydrogen to ethylene was 0.05 mol/kmol for IE1 , 2.93 mol/kmol for IE2 and 0.18 mol/kmol for IE3, the molar ratio of 1- butene to ethylene was 77 mol/kmol for IE1 , 78.9 mol/kmol for IE2 and 67.7 mol/kmol for IE3 and the molar ratio of 1-hexene to ethylene was 90.6 mol/kmol for IE1 , 95.7 mol/kmol for IE2 and 100.8 mol/kmol for IE3 The polymer production rate in the gas phase reactor was about 60 kg/h. and thus the total polymer withdrawal rate from the gas phase reactor was about 99 kg/h. The polymer had a melt flow rate MFRs of 0.69 g/10 min for IE1 , 0.78 g/10min for IE2 and 0,79 g/10min for IE3 and a density of 931.0 kg/m3 for IE1 , 931.4 kg/m3 for both IE2 and IE3 The production split (weight-% prepolymer/weight-% 1st step component/weight-% 2nd step component/weight-% 3rd step component) was about 1/19 /22 /58 .
The polymer powder was mixed under nitrogen atmosphere with 1200 ppm of Irganox B561 and 400 ppm Ca-stearate. Then it was compounded and extruded under nitrogen atmosphere to pellets by using a JSW CIMP90 twin screw extruder so that the SEI was 155 kWh/ton for IE1 , 163-164 kWh/ton for IE2 and IE3 and the melt temperature of 250 °C. The pelletised resin had a melt flow rate MFRs of 0.64 g/10 min for IE1 , 0.78 g/10min for IE2 and 0.71 g/10min for IE3, a density of 930 kg/for IE1 and 932 kg/m3 for both IE2 and IE3. They have the SHI (5/300) of 93.1 for IE1 , 74.6 for IE2 and 99.2 for IE3.
In Table 1 there is a summary polymerisation conditions and material properties for the inventive examples indicated above.
Table 1
Comparative Material CM 1
As comparative material 1 was used commercial linear low density polyethylene film grade Borstar® FX1001 having the density of 931 kg/m3 and MFRs of 0.9g/10 min. SHI(5/300)=55. Film preparation Method A
Blown films were made in 7-layer Alpine line under the following conditions: Extruder temperature settings were for all extruders: 220-230-230-230-230-235-235 in all test points.
Further the following parameters were used: Blow Up Ratio (BUR) of 3.0; frost line height of 850 0mm, which is about 3 times of die diameter (300mm); and die gap of 1 ,5mm. Layered structure of the monolayer film produced from 7-layer Alpine line of 14/14/14/14/14/15/15.
Blow Up Ratio (BUR) is defined to be Diameter of the bubble / Diameter of the die (represents TD orientation).
BUR indicates the increase in the bubble diameter over the die diameter. A blow-up ratio greater than 1 indicates that the bubble has been blown to a diameter greater than that of the die orifice. Maximum output rate (kg/h) was tested for materials at 40 micron film thickness.
Maximum output was restricted by extruder melt pressure limits. Individual throughputs of the extruders were adjusted so that in total max output (each extruder at max melt pressure) was reached. The maximum melt pressure for the Alpine line is 600 bars.
Film Sample preparation
The blown film is wound to form reels which are followed by film cutting into respective dimension for further mechanical testing.
The compositions of CM 1 and lEs were used in producing blown films at the same condition. The results from film mechanical testing are shown in table 2
Table 2
As shown above, the maximum output is improved for the inventive examples. Similarly, DDI is improved. Finally, Tear Elmendorf may be improved too.
Claims
1. A process for producing multimodal ethylene polymer film compositions comprising the steps of
(i) (co)polymerising ethylene and optionally an alpha-olefin comonomer in a first polymerisation step in the presence of a silica supported Ziegler-Natta polymerisation catalyst to produce a first ethylene homo- or copolymer (PE1) having a melt flow rate MFR2 of from 15 to 300 g/10 min;
(ii) (co)polymerising ethylene and optionally an alpha-olefin comonomer in a second
polymerisation step in the presence of the first ethylene homo- or copolymer to produce a first ethylene polymer mixture (PEM1) comprising the first ethylene homo- or copolymer and a second ethylene copolymer, said first ethylene polymer mixture having a density of from 940 to 980 kg/m3 and a melt flow rate MFR2 of from 100 to 600 g/10 min, and wherein the MFR2 0f the first ethylene homo- or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1) and the second ethylene homo- or copolymer (PE2) has a melt flow rate MFR2 of from 400 to 2000 g/10min and
(iii) copolymerising ethylene and at least one alpha-olefin comonomer in a third polymerisation step in the presence of the first ethylene polymer mixture to produce a second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture and a third ethylene copolymer (PE3), said second ethylene polymer mixture having a density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min.
2. The process according to claim 1 wherein the a-olefin comonomer is selected from the group consisting of a-olefins having from 4 to 10 carbon atoms and their mixtures, preferably from the group consisting of a-olefins having from 4 to 8 carbon atoms and their mixtures, further preferred from the group consisting of 1 -butene, 1 -hexene and 1-octene, further preferred wherein only ethylene is polymerized in the first and second polymerization steps and two comonomers are used in the third polymerization step, whereby the a-olefin comonomers in the third polymerization step are 1 -butene and 1 -hexene.
3. The process according to claim 1 or claim 2 wherein the third polymerisation step is conducted in gas phase, preferably in a gas phase fluidized bed reactor, further preferred connected in series.
4. The process according to any one of the preceding claims wherein at least one of the first and the second polymerisation step(s) is/are conducted as a slurry polymerisation in a loop
reactor, preferably both the first and the second polymerisation steps are conducted as a slurry polymerisation in two loop reactors, preferably connected in series.
5. The process according to claim 4 wherein the diluent in the slurry polymerisation comprises at least 90 % of hydrocarbons having from 3 to 5 carbon atoms.
6. The process according to any one of the preceding claims wherein the second ethylene polymer mixture (PEM2) comprises from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to < 25 % by weight of the first ethylene homo- or copolymer, from 10 to 35 % by weight, preferably 13 to 26 % by weight, further preferred > 15 to < 25 % by weight of the second ethylene homo- or copolymer and from 45 to 65 % by weight, preferably 50 to 62 % by weight, further preferred > 50 to 60 % by weight of the third ethylene copolymer.
7. The process according to any one of the preceding claims wherein second ethylene polymer mixture having a density of from 925 to 936 kg/m3, preferably 926 to 935 kg/m3, and/or a melt flow rate MFRs of from > 0.1 to 2 g/10 min, preferably 0.2 to 1 g/10min, further preferred 0.3 to < 0.8 g/10 min.
8. The process according to any one of claims 1 to 7 wherein the second ethylene polymer mixture has a density of from 927 to 936 kg/m3, preferably 926 to 935 kg/m3, the first ethylene homo- or copolymer (PE1) has a density of from 940 to 980 kg/m3 and/or a melt flow rate MFR2 of from 20 to 280 g/10 min and/or the first ethylene polymer mixture (PEM1) has a density of from 940 to 980 kg/m3 and a melt flow rate MFR2 of from 150 to 550 g/10 min.
9. The process according to any one of claims 1 to 8, wherein a ratio MFR2(PEM1) / MFR2(PE1) is between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
10. A multimodal ethylene polymer film composition having density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min and produced according to any of claim 1 to 9.
1 1. A multimodal ethylene- alpha-olefin copolymer film composition having density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min and comprising a first ethylene homo- or copolymer (PE1), a second ethylene homo- or copolymer (PE2) and a third ethylene copolymer (PE3), wherein the first ethylene homo- or copolymer (PE1) and the second ethylene homo- or copolymer (PE2) form a first ethylene polymer mixture (PEM1) and the first
ethylene polymer mixture (PEM1) and the third ethylene copolymer (PE3) form the second ethylene polymer mixture (PEM2), and wherein
IV. the first ethylene homo- or copolymer (PE1) has a melt flow rate MFR2 of from 15 to
300 g/10 min;
V. the first ethylene polymer mixture (PEM1) has a melt flow rate MFR2 of from 100 to
600 g/10 min, wherein the MFR2 0f the first ethylene homo-or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1);
VI. the second ethylene polymer mixture (PEM2) has a density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min.
12. A multimodal film composition according to claim 11 , wherein a ratio MFR2(PEM1) / MFR2(PE1) is between 1 and 60, preferably between > 1 and 5 or 2 and 30, further preferred between 1.5 and 4 or 15 and 25.
13. A process for producing a film, comprising the steps of
(i) copolymerising ethylene and an alpha-olefin comonomer in a first polymerisation step in the presence of a silica supported Ziegler-Natta polymerisation catalyst to produce a first ethylene homo- or copolymer (PE1) having a melt flow rate MFR2 of from 15 to 300 g/10 min;
(ii) copolymerising ethylene and an alpha-olefin comonomer in a second polymerisation step in the presence of the first ethylene homo- or copolymer to produce a first ethylene polymer mixture (PEM1) comprising the first ethylene homo- or copolymer and a second ethylene homo- or copolymer, said first ethylene polymer mixture having a a melt flow rate MFR2 of from 100 to 600 g/10 min, and wherein the MFR2 0f the first ethylene homo- or copolymer (PE1) is lower than first ethylene polymer mixture (PEM1) and
(iii) copolymerising ethylene and an alpha-olefin comonomer in a third polymerisation step in the presence of the first ethylene polymer mixture to produce a second ethylene polymer mixture (PEM2) comprising the first ethylene polymer mixture and a third ethylene copolymer, said second ethylene polymer mixture having a density of from 920 to 940 kg/m3 and a melt flow rate MFR5 of from 0.1 to 5 g/10 min and vi) pelletizing the second polymer mixture and
vii) providing a film by blow moulding.
14. The process according to claim 13 wherein the a-olefin comonomer is selected from the group consisting of a-olefins having from 4 to 10 carbon atoms and their mixtures, preferably from the group consisting of a-olefins having from 4 to 8 carbon atoms and their mixtures, further preferred from the group consisting of 1 -butene, 1 -hexene and 1-octene, further preferred wherein the a-olefin comonomer in the first and second polymerization steps is 1- butene and the a-olefin comonomer in the third polymerization step is 1 -butene and 1 -hexene.
15. A film comprising the multimodal film composition of claim 10 to 12.
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