WO2005097837A1 - Binuclear catalyst and process for preparation of termoelastoplastic polyolefins - Google Patents
Binuclear catalyst and process for preparation of termoelastoplastic polyolefins Download PDFInfo
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- WO2005097837A1 WO2005097837A1 PCT/RU2004/000134 RU2004000134W WO2005097837A1 WO 2005097837 A1 WO2005097837 A1 WO 2005097837A1 RU 2004000134 W RU2004000134 W RU 2004000134W WO 2005097837 A1 WO2005097837 A1 WO 2005097837A1
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- WIPO (PCT)
- Prior art keywords
- alkyl
- polymers
- range
- linear
- molecular weight
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 18
- 229920000098 polyolefin Polymers 0.000 title description 17
- 238000002360 preparation method Methods 0.000 title description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 239000012190 activator Substances 0.000 claims abstract description 20
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 7
- 229920001580 isotactic polymer Polymers 0.000 claims abstract description 7
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- 150000003624 transition metals Chemical class 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- 239000004743 Polypropylene Substances 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 229920001155 polypropylene Polymers 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 150000003623 transition metal compounds Chemical class 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 9
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001925 cycloalkenes Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 claims 1
- 238000005094 computer simulation Methods 0.000 claims 1
- 239000012634 fragment Substances 0.000 claims 1
- 238000001228 spectrum Methods 0.000 claims 1
- 229920002397 thermoplastic olefin Polymers 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000000155 melt Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100490437 Mus musculus Acvrl1 gene Proteins 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910010068 TiCl2 Inorganic materials 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000006177 alkyl benzyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
Definitions
- the present invention relates to a new catalyst combination and a process for preparing physically crosslinked recyclable thermoplastic polyolefins of simplified processability.
- the present invention relates to a new catalyst combination and a process for preparing of super high molecular weight isotactic polymers and copolymers of monomodal Gauss like molecular weight distribution with both linear and cyclic olefinically unsaturated compounds as monomer having isotacticity being within the range of from 15 to 70% of [mmmm] pentad concentration, weight average molecular weight within the range from 300,000 to 4,000,000 gms/mol, polydispersity within the range from 1.4 to 8.5 and statistic distribution of stereoscopic errors along the polymer chain.
- Thermoplastic polyolefins have been of priority interest worldwide as plastic materials for manufacturing numerous articles for several decades.
- the stereoregular isotactic polyolefins is of the particular interest in the industry due to this type of stereoregular polyolefins has the best mechanical properties compared to Sindiotactic and atactic isomers.
- thermoplastic elastomers The possibility to vary mechanical properties of different isotactic polyolefins in very broad ranges by plasticizing, blending, co polymerization and etc. allows filling almost all niches of applications in consumer products. Only one niche remains uncovered. This is the area of thermoplastic elastomers. Till the most resent study, there were no thermoplastic elastomers based on polyolefins available.
- First one is based on chemically crosslinked rubbery polymers. These polymers have the best performance, but require special methods for processing, can't be processed via methods conventional for thermoplastic polymers and, most important, all of the chemically crosslinked polymers can be processed into the article only once. An articles made from such polymers can't be reprocessed and recycling became problematic.
- Second type is plasticized PVC. It is easy to process via conventional methods and it is subjected to multiple processing, but PVC known to be very toxic on decomposition and combustion and also it gradually releases plasticizer. The toxicity issue serves as reasons to avoid application of PVC in consumer products.
- Polyolefins like polyethylene, polypropylene and copolymers found numerous applications in industry.
- the isotactic polypropylene found numerous applications in consumer products, household, packaging, motor care industry etc. due to it is the low cost thermoplastic, material having relatively good mechanical properties.
- conventional isotactic polypropylene is not the elastomer. It is the polymer of highly crystalline nature and, therefore, relatively hard with little or no impact resistance and it is suitable only for application fields in which those characteristics are desirable.
- European Patent Publication EP 0 707 016 Al specifies a catalyst composition and a process for preparing polyolefins.
- the catalysts specified in European Patent Publication EP 0 707 016 Al are the substances, made up of a metallocene compound having an indene ring and a fluorene ring which are bridged via C, Si or Ge atoms of general formula described hereinafter.
- Patent Publication EP 1 178 057 A2 and WO 02 46247 A2 which specifies a catalyst combination for preparing linear isotactic polymers where said catalyst combination containing a metal complex of general formula described hereinafter:
- R 1 - R 7 equal linear or branched Ci to C ⁇ 0 alkyl, 5- to 7-linked cycloalkyl which , in its turn, can carry one or several Ci to C 6 alkyl residues as substituent, C 6 to C ⁇ 8 aryl or arylalkyl or alkylaryl, in which case R'/R 2 , R 3 / R 4 , R 6 /R 7 can be partially or simultaneously integrated into 5- to 7-linked cycloalkyl or aryl rings fused thereto;
- E 1.2-ethyl, 1.3-propyl, 1.4-butyl, or - carbon, silicon, germanium optionally with
- R9, RIO equal CI to C8 alkyl, 4- to 7-linked cycloalkyl, aryl, in which case R9, RIO can, jointly with E, form a 4- to 7-linked cycloalkyl or aryl;
- E 2 C 2 , therewith, signifies oxygen or sulphur and n is 1 or 2;
- R 1 ' Ci to C alkyl, aryl, Ci to C 8 oxyalkyl, , C, to C 8 trialkylsiloxy;
- M titanium, zirconium, hafnium, vanadium, niobium, tantalum;
- X halogen orCi to C 8 alkyl, aryl, benzyl;
- the metallocene catalysts according to European Patent publications EP 1 178 057 A2 and WO 02 46247 A2 are accompanied with methylalumoxan activator (MAO).
- the polymers prepared according to the EP 1 178 057 A2 and WO 02 46247 A2 are linear, thermoplastic, elastic polymers made from an olefinically unsaturated compound with an isotactic arrangement of the monomer units and a statistic distribution of isolated stereoscopic errors along the individual chains.
- the average molecular weight Mw of the polymers is in the range of from 100,000 to 800,000 gms/mol.
- the glass transition temperature is in the range from -50 to +30.
- the most essential for the polymer prepared according to the EPA is the following: • Stereoscopic errors are isolated and obligatory has neighboring isotactic units.
- Catalyst is of metallocene type providing insertion mechanism of polymerization • Narrow molecular mass distribution independently from the average molecular weight of the polymer obtained resulting from type of catalyst and mechanism of polymerization. • Catalyst is very much sensitive to residual amount of the moisture in the polymerization medium. Because of these inherent disadvantages of the process according to the invention described in the EPA the polymer obtained according to the said invention has shortcomings mentioned below.
- the low and middle molecular weight polymer of narrow molecular weight distribution (n ⁇ 2.5) and with Mw up to 500,000 gms/mol can be processed from the melt via conventional methods like blow molding, ram-extrusion, compression molding etc.
- o melt viscosity
- isotactic polyolefins if contains low concentration of stereo errors, are stil brittle materials due to too high rystallinity. Increasing the concentration of stereo errors makes it more amorphous and elastic, but at the same time it become sticky and can't be used. Stickiness disappears with further growth of average molecular weight, however high molecular weight polymer can't be processed from the melt due to very high viscosity of the melt. Viscosity of the melt increases with the growth of molecular weight of polymer.
- the object of the present invention is the novel catalyst combination of non-metallocene type, the process to make polymers from olefinically unsaturated compounds using herein catalyst combination, and polyolefins obtained including but not limited the physically crosslinked polyolefins demonstrating thermoplastic and thermoplastic- elastic properties.
- the polymers by present invention may be obtained in the sticky form, but also not sticky.
- the polymers are easy processable from the melt and, thus, being applicable for many application fields. That object is in regard of the catalyst combination, solved by the characterizing features of Claim 1 ; in regards to the process for preparing the polymers, the characterizing features of Claim 4 solve it.
- First aspect of the present invention is the novel catalyst combination containing a transition metal compound and an activator.
- transition metal compound is organometalic compound, comprising the phenoxyimine type organic ligand and a metal atom one from those of Fourth Auxiliary Group of the Periodic System Table IVB able to form formally positively charged polymerization initiation site located on the metal atom following interaction with an activator.
- Titanium, zirconium and hafnium are preferably suitable as the metal atoms.
- the transition metal compound according to the invention contains either halogen or a Ci - C 3 alkyl aryl or benzyl residues bonded to metal atom at the position X, however there are eliminated by an activator resulting positively charged polymerization site of the catalyst at the initial stage of the polymerization process described hereinafter.
- transition metal containing organometalic compound hereinafter called a transition metal compound may be represented by the Formula III:
- M - metal of the Fourth Auxiliary Group of the Periodic System preferably titanium, zirconium, hafnium, vanadium, niobium or tantalum; X - halogen or a C ⁇ - C 3 liner or branched alkyl, aryl or benzyl X 2 - halogen or a Ci - C liner or branched alkyl, aryl or benzyl R' - H or halogen or a linear or branched Ci - C alkyl, R 2 - H or halogen or a linear or branched Ci - C alkyl, R 3 - H or halogen or a linear or branched C ⁇ - C 4 alkyl, R 4 - H or halogen or a linear or branched Ci - C 4 alkyl, and an activator.
- the activator may be an open-chain or cyclic alumoxane compound of general Formula IV or V, such as is reflected hereinafter:
- R 7 is a Ci - C 4 alkyl group and n is a number between 5 and 30.
- the invention furthermore, provides the process for preparing linear, thermoplastic-elastic polymers from olefinically unsaturated compounds with an isotactic arrangement of the monomer unit and a statistic distribution of isolated stereoscopic errors along the individual chains, tacticity varying within the range of between 15 and 70 % [mmmm] pentad concentration. A regular sequence of isotactic and atactic blocks, therewith, is excluded.
- the process according to the invention is specifically characterized in that a specially selected catalyst combination is used as described before.
- Favorable temperatures are within the range of from -50 °C to 200 °C, of preference at from 100 to 150 °C and of high preference at from 20 to 50 °C.
- the polymerization reactions can be carried out in the gas phase, in suspension and in supercritical monomers and especially in solvents inert under polymerization conditions.
- the polymerization in the liquid propylene as the solvent and slurry process has proven to be the clearly superior thing for the present preparation process.
- the inert solvents are particularly suitable for such process.
- Inert solvents herein are such solvents that do not contain any reactive groups in the molecule, i.e. aromatic solvents like benzene, toluene, xylene, ethylbenzene or alkanes such as e.g. propane, n-butane ; i-butane. pentane, hexane, heptane or mixtures thereof.
- aromatic solvents like benzene, toluene, xylene, ethylbenzene or alkanes
- propane n-butane
- i-butane i-butane. pentane, hexane, heptane or mixtures thereof.
- the invention furthermore, provides the linear, thermoplastic, elastic polymers from an olefinically unsaturated compound with an isotactic arrangement of the monomer units and a statistic distribution of isolated stereoscopic errors along the individual chains and a mean molecular weight
- Mw of the polymers within the range of from 300,000 to 4,000,000 gms/mol and a TG of from -50 to +30.
- the linear, isotactic polymers according to the present invention have a molecular weight within the range of from 300,000 to 4,000,000, of preference from 700,000 to 2,500,000 and of special preference within the range of from 1,000,000 to 2,000,000 gms/mol.
- the polydispersity coefficient generally amounts within the range from 1.4 to 8.5.
- the molecular weight distribution of the polymer according to the invention may be polymodal, however preferably it is the monomodal, Gauss like type.
- the relatively high polydispersity provides polymer with improved processability from the melt.
- Low molecular weight fractions serve as lubricant preventing entangling of big molecules and thus decreasing zero share viscosity of the melt and melt index.
- the polymers show a glass transition temperature Tg within the range of from -50 °C to +30 °C, of special preference a Tg of from -20 °C to +10 °C.
- the linear, isotactic polymers prepared according to the invention present a structure of one or several C 2 - C 2 o olefins.
- the olefin is preferred to be a C 3 - C o - Alk-1 -ene.
- Examples of such C 3 - C 2 o -Alk-1 -enes are: propene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1 -octene, 1- nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-eicosene.
- C 5 - C 2 o cycloolefins are of the especially suitable kind. Examples thereof are cyclopentene, cyclohexene, norbornadiene and its derivatives.
- polypropylene is especially preferred.
- Further suitable polymers are copolymers from propylene and a C - C o olefin or a cycloolefin. It is also possible to prepare terpolymers which show the characteristics defined in Claim 1 of present invention when they present a structure of propylene, a C 2 - C o olefin and a cycloolefin.
- the polymers prepared according to the invention has a distinct elastic properties due to it's specific morphology comprises microcrystalline domains surrounded with areas of elastic amorphous polymer. Due to its morphology, it can be classified as Physically Crosslinked polymer. Crystals serve as the cross linkages or lattice points of the net type structure. Amorphous areas provide to polymer with elasticity while crystalline domains prevent forced viscous flow of the polymer providing good reset. The crystalline phase possess to melting on processing resulting conventional melt of none-crosslincked polymer. The process is reversible and after crystallization on processing the polymer restores initial morphology and mechanical properties.
- the polymers prepared according to the invention show a distinct elastic behavior in a tensile-strength test, measured with a "Standard Universal Testing Machine Instron-1 122".
- a melting temperature measured by means of the "Differential Scanning Calorimetry” (DSC) method within the range of from -50 °C to 250 °C.
- DSC Different Scanning Calorimetry
- the polymer according to the invention clearly differ in regard of their elastic-thermoplastic behavior, from the state-of-the-art, i.e. from European Printed Publication 0 707 016 Al mentioned in the state of art.
- the polymers prepared according to the present invention are particularly suitable for the manufacture of articles of relatively good deformation resistance, such as e.g. sheathings for household appliances.
- the polymers can be used in polymer mixtures for impact resistance modification. Due to their elastic characteristics, the polymers are especially suited for elastic sheets, cable insulation, filaments, flat materials including nonwoven materials, films, foams, coatings, molded bodies, gaskets.
- IR spectra were recorded using with a Magna-IR 750 spectrophotometer.
- Measurements were made using Waters 150-C instrument equipped with a linear HT- ⁇ -styragel column calibrated with both polypropylene and polystyrene standards and 1,2-dichiorobenzene as a solvent.
- the glass transition temperature was determined by means of the "Differential Scanning
- the two neck flask was filled with 20 ml of toluene, 0,1990 g (0.85 mmol) of 3,5-di-tert- butylsalicylic aldehyde, 0,0017 g (0.01 mmol) of p-toluenesulfonic acid and 0,1503 g (0.43 mmol) of l ,r-perfluorodiphenile.
- the mixture was heated with reflux for 20 hours, then solution was cooled to ambient temperature, filtered and the solvent was removed in vacuum resulting deep yellow oil.
- the product was dissolved in 20 ml of mixture hexane-ethyl acetate (5:1) and purified by column chromatography using silica gel as absorbent and the mixture of hexane-ethyl acetate (5:1) as the eluent resulting 0,5305 g of yellow oil.
- Example N°2 The 250 ml stainless steel reactor was evacuated with following flushing with dry argon for several times for replacement of air and moisture then it was filled with 100 ml of dry toluene. 1.9 mmol of MAO in form of 10% solution in toluene was injected into reactor and argon was replaced with ethylene to maintain pressure at 1 1 atm. In 5-10 min on reaching the saturation of ethylene dissolution at 11 atm and 30oC the polymerization was initiated by injection of 0.5 ml of solution containing 3.8 ⁇ mol maintaining molar ratio AI MAO /TI molar is equal 500 mol/mol.
- Example JV°4 Propylene polymerization has been carried out in the medium of liquid propylene in stainless steel reactor (200 ml) under rigorous stirring of reaction medium.
- the 200 ml stainless steel reactor equipped with mechanical stirrer was heated to 70°C for 1.5 hours with continues pumping out the residues of moisture and air then it was cooled to ambient temperature and purged with gaseous propylene with following filling with 50 ml of liquid propylene.
- the reactor was heated to 50°C maintaining pressure of 40 atm and 1 ,35 ml of 10% solution of MAO (10.35 mmol) in toluene was injected.
- glass ampoule containing 3,952 mg (2.2 ⁇ mol) of bis[4,4'-bis-(3,5-di-tert- butylsalicyIidene)perfluorodipheniIe]titanium(IV) dichloride was injected into reactor with following braking with special plunger.
- the polymerization was stopped by venting of propylene following injection of ethanol into the reaction medium giving 5.0 g of polypropylene.
- Example N°5 Propylene polymerization has been carried out in the medium of liquid propylene in stainless steel reactor (200 ml) under rigorous stirring of reaction medium.
- the 200 ml stainless steel reactor equipped with mechanical stirrer was heated to 70°C for 1.5 hours with continues pumping out the residues of moisture and air then it was cooled to ambient temperature and purged with gaseous propylene with following filling with 50 ml of liquid propylene.
- M w 9872000 g/mol
- M w /M n 8.8.
- Physico mechanical properties of PP sample elasticity modulus 4.3 MPa, rupture stress >0.8 MPa, elongation at rupture > 1800 %, recovery set after 300 % elongation 6.7 % (Fig.3).
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Abstract
A catalyst combination ana a process for preparing physically crosslinked recyclable thermoplastic polyolefins of simplified processability. In particular the new catalyst combination and a process are useful and for preparing of super high molecular weight isotactic polymers and copolymers of monomodal Gauss like molecular weight distribution with both linear and cyclic olefinically unsaturated compounds as monomer having isotacticity being within the range of from 15 to 70% of [mmmm] pentad concentration, weight average molecular weight within the range from 300,000 to 4,000,000 gms/mol, polydispersity within the range from 1.4 to 12 and statistic distribution of stereoscopic errors along the polymer chain. The catalyst comprises bisphenoxyimine type complexes of transition metals in combination with MAO type activator.
Description
Binuclear catalyst and process for preparation of termoelastoplastic polyolefins
Field of the invention
The present invention relates to a new catalyst combination and a process for preparing physically crosslinked recyclable thermoplastic polyolefins of simplified processability. In particular the present invention relates to a new catalyst combination and a process for preparing of super high molecular weight isotactic polymers and copolymers of monomodal Gauss like molecular weight distribution with both linear and cyclic olefinically unsaturated compounds as monomer having isotacticity being within the range of from 15 to 70% of [mmmm] pentad concentration, weight average molecular weight within the range from 300,000 to 4,000,000 gms/mol, polydispersity within the range from 1.4 to 8.5 and statistic distribution of stereoscopic errors along the polymer chain.
Scope of the invention
Thermoplastic polyolefins have been of priority interest worldwide as plastic materials for manufacturing numerous articles for several decades. The stereoregular isotactic polyolefins, is of the particular interest in the industry due to this type of stereoregular polyolefins has the best mechanical properties compared to sindiotactic and atactic isomers.
The possibility to vary mechanical properties of different isotactic polyolefins in very broad ranges by plasticizing, blending, co polymerization and etc. allows filling almost all niches of applications in consumer products. Only one niche remains uncovered. This is the area of thermoplastic elastomers. Till the most resent study, there were no thermoplastic elastomers based on polyolefins available.
Three general types of elastomers are widely used in the industry nowadays.
First one is based on chemically crosslinked rubbery polymers. These polymers have the best performance, but require special methods for processing, can't be processed via methods conventional for thermoplastic polymers and, most important, all of the chemically crosslinked polymers can be processed into the article only once. An articles made from such polymers can't be reprocessed and recycling became problematic.
Second type is plasticized PVC. It is easy to process via conventional methods and it is subjected to multiple processing, but PVC known to be very toxic on decomposition and combustion and also it gradually releases plasticizer. The toxicity issue serves as reasons to avoid application of PVC in consumer products.
Third type is EPDM like copolymers. It is much easy to process these polymers compared to processing of cross-linked rubbery polymers, but anyway it is the copolymers and it can't be reprocessed. Recycling remains big issue.
Polyolefins like polyethylene, polypropylene and copolymers found numerous applications in industry. In particular the isotactic polypropylene found numerous applications in consumer products, household, packaging, motor care industry etc. due to it is the low cost thermoplastic, material having relatively good mechanical properties. Also it is very important that it is recyclable polymer, which can be re-processed for several times. However conventional isotactic polypropylene is not the elastomer. It is the polymer of highly crystalline nature and, therefore, relatively hard with little or no impact resistance and it is suitable only for application fields in which those characteristics are desirable.
Various attempts have been made, aiming to improve elasticity of polypropylene based material by controlling the crystallinity. Both isotactic and sindiotactic polypropylenes are highly crystalline polymers. Sindiotactic polypropylene is brittle polymer of high Tg and Tm close to decomposition temperature. It didn't find an application in the industry due to rapid decomposition on processing. In opposite the atactic polypropylene is completely amorphous liquid polymer. However the attempt to control crystallinity and improve elasticity by simply blending of crystalline types of polypropylene with the amorphous atactic one is fail. These polymers are completely immiscible and phase separation in the blend results fail in mechanical properties.
Most recently, it has been made attempt to decrease crystallinity of polypropylene by control of tacticity of said polymer during process of polymerization.
Background Art
European Patent Publication EP 0 707 016 Al specifies a catalyst composition and a process for preparing polyolefins. The catalysts specified in European Patent Publication EP 0 707 016 Al are the substances, made up of a metallocene compound having an indene ring and a fluorene ring which are bridged via C, Si or Ge atoms of general formula described hereinafter.
It is essential that, in the indene ring system at least the moiety denoted with R4 not to be the hydrogen. When that moiety R4 is hydrogen, the effects, such as specified in the aforementioned European Patent Publication will not be attained (P 6, from L 57 up to P 7, L 3). The polymers specified in European Patent Publication EP 0 707 016 A l have been prepared with these metallocene type catalyst. The polypropylene also can be prepared with those metallocene catalysts, however, the polypropylene described in the European Patent Publication EP 0 707 016 Al is not the elastic one. The characteristics of all polyolefins described in the European Patent Publication EP 0 707 016 Al are unsatisfactory in regard to their elastic behavior as it can be drawn from the examples and the graphs mentioned in the patent.
The most close to the object of present invention is that described in Patent Publication EP 1 178 057 A2 and WO 02 46247 A2 which specifies a catalyst combination for preparing linear isotactic polymers where said catalyst combination containing a metal complex of general formula described hereinafter:
R1 - R7 equal linear or branched Ci to Cι0 alkyl, 5- to 7-linked cycloalkyl which, in its turn, can carry one or several Ci to C6 alkyl residues as substituent, C6 to Cι8 aryl or arylalkyl or alkylaryl, in which case R'/R2, R3/ R4, R6/R7 can be partially or simultaneously integrated into 5- to 7-linked cycloalkyl or aryl rings fused thereto;
E equal 1.2-ethyl, 1.3-propyl, 1.4-butyl, or - carbon, silicon, germanium optionally with
R9, RIO equal CI to C8 alkyl, 4- to 7-linked cycloalkyl, aryl, in which case R9, RIO can, jointly with E, form a 4- to 7-linked cycloalkyl or aryl;
E2 = C2, therewith, signifies oxygen or sulphur and n is 1 or 2;
R1 ' equal Ci to C alkyl, aryl, Ci to C8 oxyalkyl, , C, to C8 trialkylsiloxy; M equal titanium, zirconium, hafnium, vanadium, niobium, tantalum; X equal halogen orCi to C8 alkyl, aryl, benzyl;
The metallocene catalysts according to European Patent publications EP 1 178 057 A2 and WO 02 46247 A2 are accompanied with methylalumoxan activator (MAO).
The polymers prepared according to the EP 1 178 057 A2 and WO 02 46247 A2 are linear, thermoplastic, elastic polymers made from an olefinically unsaturated compound with an isotactic arrangement of the monomer units and a statistic distribution of isolated stereoscopic errors along the individual chains. The average molecular weight Mw of the polymers is in the range of from 100,000 to 800,000 gms/mol. The glass transition temperature is in the range from -50 to +30. The most essential for the polymer prepared according to the EPA is the following: • Stereoscopic errors are isolated and obligatory has neighboring isotactic units. • Catalyst is of metallocene type providing insertion mechanism of polymerization • Narrow molecular mass distribution independently from the average molecular weight of the polymer obtained resulting from type of catalyst and mechanism of polymerization. • Catalyst is very much sensitive to residual amount of the moisture in the polymerization medium.
Because of these inherent disadvantages of the process according to the invention described in the EPA the polymer obtained according to the said invention has shortcomings mentioned below. The low and middle molecular weight polymer of narrow molecular weight distribution (n<2.5) and with Mw up to 500,000 gms/mol can be processed from the melt via conventional methods like blow molding, ram-extrusion, compression molding etc. and has acceptable melt viscosity characterized with acceptable value of zero share melt viscosity T|o. However such isotactic polyolefins, if contains low concentration of stereo errors, are stil brittle materials due to too high rystallinity. Increasing the concentration of stereo errors makes it more amorphous and elastic, but at the same time it become sticky and can't be used. Stickiness disappears with further growth of average molecular weight, however high molecular weight polymer can't be processed from the melt due to very high viscosity of the melt. Viscosity of the melt increases with the growth of molecular weight of polymer. Till the molecular weight is lower them a critical value Mw<Mc the melt viscosity grow linearly with growth of weight average molecular weight (ηo~kMw), however for polymers possessing higher molecular weight (Mw>Mc) the dependence become rather strong (ηo∞Mw ' ). The difference is related to the ability of long chains to entangle which imposes melt a restriction to ease flow. The critical value of weight average molecular weight for elastic polypropylene is close to 350,000 gms/mol while polymer is stil sticky. Further growth of Mw up to values of Mw>500,000 gms/mol results non-sticky polymer, however entangling of macromolecules in the melt results too high viscosity disabling processing. Actually it is a dilemma: Low Mw - sticky polymer, high Mw - difficult to process.
This is not the case for polymers with broad molecular weight distribution (n>3) or polymer blends comprising admixture of low Mw polymer or of plasticised polymers where relatively small molecules of low Mw fractions serve as a lubricants preventing entangling of large macromolecules. However narrow molecular weight polyolefins obtained using metallocene catalysts according to the EP 1 178 057 A2 and WO 02 46247 A2 are almost immiscible with other types of polyolefins and even with the same type of polyolefin of low Mw. It makes impossible to provide high Mw polyolefins with melt processability via blending.
Disclosure of the invention
Departing from all these facts described in the art the object of the present invention is the novel catalyst combination of non-metallocene type, the process to make polymers from olefinically
unsaturated compounds using herein catalyst combination, and polyolefins obtained including but not limited the physically crosslinked polyolefins demonstrating thermoplastic and thermoplastic- elastic properties. The polymers by present invention may be obtained in the sticky form, but also not sticky. The polymers are easy processable from the melt and, thus, being applicable for many application fields. That object is in regard of the catalyst combination, solved by the characterizing features of Claim 1 ; in regards to the process for preparing the polymers, the characterizing features of Claim 4 solve it. First aspect of the present invention First aspect of the present invention is the novel catalyst combination containing a transition metal compound and an activator.
Herein after the transition metal compound is organometalic compound, comprising the phenoxyimine type organic ligand and a metal atom one from those of Fourth Auxiliary Group of the Periodic System Table IVB able to form formally positively charged polymerization initiation site located on the metal atom following interaction with an activator. Titanium, zirconium and hafnium are preferably suitable as the metal atoms.
Initially the transition metal compound according to the invention contains either halogen or a Ci - C3 alkyl aryl or benzyl residues bonded to metal atom at the position X, however there are eliminated by an activator resulting positively charged polymerization site of the catalyst at the initial stage of the polymerization process described hereinafter.
The transition metal containing organometalic compound hereinafter called a transition metal compound may be represented by the Formula III:
M - metal of the Fourth Auxiliary Group of the Periodic System, preferably titanium, zirconium, hafnium, vanadium, niobium or tantalum;
X - halogen or a C\ - C3 liner or branched alkyl, aryl or benzyl X2 - halogen or a Ci - C liner or branched alkyl, aryl or benzyl R' - H or halogen or a linear or branched Ci - C alkyl, R2 - H or halogen or a linear or branched Ci - C alkyl, R3 - H or halogen or a linear or branched C\ - C4 alkyl, R4 - H or halogen or a linear or branched Ci - C4 alkyl, and an activator.
As defined in Claim 1 of present invention, it certainly is furthermore provided in accordance with the invention, to additionally use at least one activator, apart from the transition metal compound specified above. European Printed Publication 1 178 057 A2 and WO 02 46247 A2 have also specified such activators and the invention, herewith, also encompasses all the activators that are known in the state-of-the-art as a co-catalysts for metallocene compounds, however in the present invention these activators are reapplied to the novel family of catalysts of phenoxyimine type specified above as the transition metal compound. At least one compound of genera Formulas II to VI is, however used with special preference. Accordingly, the activator may be an open-chain or cyclic alumoxane compound of general Formula IV or V, such as is reflected hereinafter:
R7 R7 (IV) (Al-O-)„ (V) (Al-O-)„
wherein R7 is a Ci - C4 alkyl group and n is a number between 5 and 30.
In case of the catalyst combination according to the invention, also the above-specified compounds of general Formulas IV and V can, alone or in combination with the subsequent activators such as those reflected by general Formulas IV to VI, be used. B(C6F5)3 (VI) R8 3C[B(C6F5)4] (VII)
[R8 3NH][B(C6F5)4] (VIII) In general, Formulas VI to VIII, R , signifies a Ci - C alkyl group or an aryl group. It has, therewith, proven to be especially favorable when the transition metal compound according to general Formula III and the activator according to general Formulas IV to VIII are employed in such quantities that the atomic ratio between aluminium from the alumoxane or boron from the cationic
activator and the transition metal from the transition metal compound specified below is within the range of from 1 : 1 to 106: 1. Second aspect of the present invention
The invention, furthermore, provides the process for preparing linear, thermoplastic-elastic polymers from olefinically unsaturated compounds with an isotactic arrangement of the monomer unit and a statistic distribution of isolated stereoscopic errors along the individual chains, tacticity varying within the range of between 15 and 70 % [mmmm] pentad concentration. A regular sequence of isotactic and atactic blocks, therewith, is excluded. The process according to the invention is specifically characterized in that a specially selected catalyst combination is used as described before.
Pressures of from 1 to 100 bars, preferably of from 3 to 20 bars and in particular of from 5 to 15 bars, have proven to be suitable reaction parameters for preparing the linear thermoplastic, elastic olefin polymers. Favorable temperatures are within the range of from -50 °C to 200 °C, of preference at from 100 to 150 °C and of high preference at from 20 to 50 °C. The polymerization reactions can be carried out in the gas phase, in suspension and in supercritical monomers and especially in solvents inert under polymerization conditions. In particular the polymerization in the liquid propylene as the solvent and slurry process has proven to be the clearly superior thing for the present preparation process. The inert solvents are particularly suitable for such process. Inert solvents herein are such solvents that do not contain any reactive groups in the molecule, i.e. aromatic solvents like benzene, toluene, xylene, ethylbenzene or alkanes such as e.g. propane, n-butane; i-butane. pentane, hexane, heptane or mixtures thereof.
Third aspect of the present invention
The invention, furthermore, provides the linear, thermoplastic, elastic polymers from an olefinically unsaturated compound with an isotactic arrangement of the monomer units and a statistic distribution of isolated stereoscopic errors along the individual chains and a mean molecular weight
Mw of the polymers within the range of from 300,000 to 4,000,000 gms/mol and a TG of from -50 to +30.
With the polymer prepared according to the invention, it is essential that the stereoscopic errors be situated along the main backbone of the polymeric chain.
Apart from the above-mentioned stereoscopic errors distribution along the polymeric chain the linear, isotactic polymers according to the present invention have a molecular weight within the
range of from 300,000 to 4,000,000, of preference from 700,000 to 2,500,000 and of special preference within the range of from 1,000,000 to 2,000,000 gms/mol.
The molecular weight distribution and polydispersity coefficient n=Mw/Mn (weight average molecular weight value/number average molecular weight) of the polymers according to the present invention are of the particular importance. The polydispersity coefficient generally amounts within the range from 1.4 to 8.5. The molecular weight distribution of the polymer according to the invention may be polymodal, however preferably it is the monomodal, Gauss like type. The relatively high polydispersity provides polymer with improved processability from the melt. Low molecular weight fractions serve as lubricant preventing entangling of big molecules and thus decreasing zero share viscosity of the melt and melt index.
In addition to all that, the polymers show a glass transition temperature Tg within the range of from -50 °C to +30 °C, of special preference a Tg of from -20 °C to +10 °C.
The linear, isotactic polymers prepared according to the invention present a structure of one or several C2 - C2o olefins. In this case, the olefin is preferred to be a C3 - C o - Alk-1 -ene. Examples of such C3 - C2o -Alk-1 -enes are: propene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1 -octene, 1- nonene, 1-decene, 1-dodecene, 1-hexadecene, 1-octadecene, 1-eicosene.
Apart from the already mentioned olefins, also C5 - C2o cycloolefins are of the especially suitable kind. Examples thereof are cyclopentene, cyclohexene, norbornadiene and its derivatives. In case of the linear, isotactic polymers, polypropylene is especially preferred. Further suitable polymers are copolymers from propylene and a C - C o olefin or a cycloolefin. It is also possible to prepare terpolymers which show the characteristics defined in Claim 1 of present invention when they present a structure of propylene, a C2 - C o olefin and a cycloolefin.
The polymers prepared according to the invention has a distinct elastic properties due to it's specific morphology comprises microcrystalline domains surrounded with areas of elastic amorphous polymer. Due to its morphology, it can be classified as Physically Crosslinked polymer. Crystals serve as the cross linkages or lattice points of the net type structure. Amorphous areas provide to polymer with elasticity while crystalline domains prevent forced viscous flow of the polymer providing good reset. The crystalline phase possess to melting on processing resulting conventional melt of none-crosslincked polymer. The process is reversible and after crystallization on processing the polymer restores initial morphology and mechanical properties. The polymers prepared according to the invention show a distinct elastic behavior in a tensile-strength test, measured with a "Standard Universal Testing Machine Instron-1 122". A melting temperature, measured by means of the "Differential Scanning Calorimetry" (DSC) method within the range of from -50 °C to 250 °C.
The polymer according to the invention clearly differ in regard of their elastic-thermoplastic behavior, from the state-of-the-art, i.e. from European Printed Publication 0 707 016 Al mentioned in the state of art. The polymers prepared according to the present invention are particularly suitable for the manufacture of articles of relatively good deformation resistance, such as e.g. sheathings for household appliances. Furthermore, it is worth mentioning that the polymers can be used in polymer mixtures for impact resistance modification. Due to their elastic characteristics, the polymers are especially suited for elastic sheets, cable insulation, filaments, flat materials including nonwoven materials, films, foams, coatings, molded bodies, gaskets.
The invention can be illustrated with the following examples Methods applied
The NMR spectra of the polymers were recorded at 1 10°C on a Bruker AC-200 instrument using
1 ,1,2,2-tetrachloroethane-Gk as the solvent. The concentration of polymer in the solution was 7.5% w/w.
The NMR spectra of ligands and catalysts were recorded at ambient temperature using a Bruker
AMX -400 instrument and chloroform - CDC13 as a solvent.
IR spectra were recorded using with a Magna-IR 750 spectrophotometer.
The molecular weight distribution, the weight average molecular weights Mw, the number average molecular weight Mn and polydispersity coefficient n=Mw/Mn of the polymers were measured by the gel permeation chromatography (GPC) method at 135°C with microstyragel as column material.
Measurements were made using Waters 150-C instrument equipped with a linear HT-μ-styragel column calibrated with both polypropylene and polystyrene standards and 1,2-dichiorobenzene as a solvent.
The glass transition temperature was determined by means of the "Differential Scanning
Calorimetry" (DSC) method.
Mechanical properties and elasticity were determined in a tensile-strength test, measured with a
Instron-1 122 machine.
The polymerization experiments were carried out in 250 ml stainless still reactor under the conditions described below.
X-ray powder diffraction analysis of PP samples was carried out on a DRON-2 diffractometer.
Preparation of catalyst
Preparation of 4,4'-bis(3,5-di-tert-butylsaIicylidene)- 2,2',3,3',5,5',6,6'-perfluorodipheny.e
50 ml the two neck flask was filled with 20 ml of toluene, 0,1990 g (0.85 mmol) of 3,5-di-tert- butylsalicylic aldehyde, 0,0017 g (0.01 mmol) of p-toluenesulfonic acid and 0,1503 g (0.43 mmol) of l ,r-perfluorodiphenile. The mixture was heated with reflux for 20 hours, then solution was cooled to ambient temperature, filtered and the solvent was removed in vacuum resulting deep yellow oil. The product was dissolved in 20 ml of mixture hexane-ethyl acetate (5:1) and purified by column chromatography using silica gel as absorbent and the mixture of hexane-ethyl acetate (5:1) as the eluent resulting 0,5305 g of yellow oil.
Yield 0,7228 mmol (82 %), 1H NMR: : δ 1,46 (d, 72H, tert-Bu), 7.05 (4H, aromatic H), 7.36 (4H, aromatic H), 8,84 (s, 2H, CH=N), 11.79 (s, 2H, OH). IR: v/cm"1: (C=N) 1690. Analysis found (%): C, 66,29; H, 5,70; N, 3,62. Calculated for C42H44N OF4 (%): C, 66,31; H, 5,83; N, 3,68.
Preparation of bis[4,4'-bis-(3,5-di-tert-butylsalicyIidene)perfluorodiphenile]titanium(IV) dichloride
50ml three-neck flask equipped with mechanical stirrer, argon inlet tube and dosing funnel was purged with dry argon and charged with solution containing 0,0800 g (0.10 mmol) of 4,4'-bis-(3,5- di-tert-butylsalicylidene)perfluorodiphenile dissolved in 10 ml of methylene chloride. The solution containing 0,0240 g (0.10 mmol) of TiCl2(O Pr)2 in 15 ml of methylene chloride was added dropwise with stirring. The mixture was agitated for 20 hours at ambient temperature; solid product was filtered out from reaction mixture, washed with methylene chloride and toluene and dried in vacuum at 60°C to remove residues of solvent with following purging with dry argon to give 0,0784 g of crystalline product.
Yield 0,0447 mmol (85%), IR, v/cm-1: (C=N) 1610; (Ti-O) 566, (Ti-N) 472, (Ti-Cl) 420, 397; Η NMR: δ 1,54 (d, 144H, t-Bu), 7,05 (m, 8H, aromatic H), 7,36 (m, 8H, aromatic H), 8,93 (s, 4H, CH=N). Analysis found (%):C, 57.40; H, 4.86; N, 3.03; Ti, 5.42; CI, 7.98. Calculated for Ti2C84H12N4O4Fι6Cl4 (%):C, 57.48; H, 4.82; N, 3.19; Ti, 5.45; CI, 8.08.
Polymerization Polymerization of ethylene Example N°l The 250 ml stainless steel reactor was evacuated with following flushing with dry argon for several times for replacement of air and moisture then it was filled with 100 ml of dry toluene. 7.6 mmol of MAO in form of 10% solution in toluene was injected into reactor and argon was replaced with ethylene to maintain pressure at 1 1 atm. In 5-10 min on reaching the saturation of ethylene dissolution at 1 1 atm and 30oC the polymerization was initiated by injection of 0.5 ml of solution containing 3.8 μmol maintaining molar ratio AIMAO/ J molar is equal 2000 mol/mol. Polymerization was conducted for 10 min then reactor was depressurized, residual ethylene was removed by purging with argon, then 20 ml of ethanol containing of 2% wt of HC1 was added for neutralization of catalyst, the solvent was evaporated in vacuum. The polymer was washed with ethanol/water mixture and dried to in vacuum at 60 °C resulting 12.3 g of polyethylene with Tm=142oC according to DSC. Example N°2 The 250 ml stainless steel reactor was evacuated with following flushing with dry argon for several times for replacement of air and moisture then it was filled with 100 ml of dry toluene. 1.9 mmol of MAO in form of 10% solution in toluene was injected into reactor and argon was replaced with ethylene to maintain pressure at 1 1 atm. In 5-10 min on reaching the saturation of ethylene dissolution at 11 atm and 30oC the polymerization was initiated by injection of 0.5 ml of solution containing 3.8 μmol maintaining molar ratio AIMAO/TI molar is equal 500 mol/mol. Polymerization was conducted for 10 min then reactor was depressurized, residual ethylene was removed by purging with argon, then 20 ml of ethanol containing of 2% wt of HC1 was added for neutralization of catalyst, the solvent was evaporated in vacuum. The polymer was washed with ethanol/water mixture. The residues of the solvent were removed in vacuum at 60 °C resulting 13.4 g of polyethylene with Tm=142oC according to DSC. Example N°3 The 250 ml stainless steel reactor was evacuated with following flushing with dry argon for several times for replacement of air and moisture then it was filled with 100 ml of dry heptane. 1.9 mmol of MAO in form of 10% solution in toluene was injected into reactor and argon was replaced with ethylene to maintain pressure at 1 1 atm. In 5-10 min on reaching the saturation of ethylene dissolution at 1 1 atm and 30oC the polymerization was initiated by injection of 0.5 ml of solution
containing 3.8 μmol maintaining molar ratio AlMAθ/Ti molar is equal 500 mol/mol. Polymerization was conducted for 10 min then reactor was depressurized, residual ethylene was removed by purging with argon, then 20 ml of ethanol containing of 2% wt of HC1 was added to the suspension with intensive stirring for neutralization of catalyst, the solvent mixture was evaporated in vacuum. The polymer was washed with ethanol/water mixture. The residues of the solvent were removed in vacuum at 60 °C resulting 8.3 g of polyethylene with Tm=133oC according to DSC.
Polymerization of propylene
Example JV°4 Propylene polymerization has been carried out in the medium of liquid propylene in stainless steel reactor (200 ml) under rigorous stirring of reaction medium. The 200 ml stainless steel reactor equipped with mechanical stirrer was heated to 70°C for 1.5 hours with continues pumping out the residues of moisture and air then it was cooled to ambient temperature and purged with gaseous propylene with following filling with 50 ml of liquid propylene. The reactor was heated to 50°C maintaining pressure of 40 atm and 1 ,35 ml of 10% solution of MAO (10.35 mmol) in toluene was injected. Then glass ampoule containing 3,952 mg (2.2 μmol) of bis[4,4'-bis-(3,5-di-tert- butylsalicyIidene)perfluorodipheniIe]titanium(IV) dichloride was injected into reactor with following braking with special plunger. In 1 .5 hour the polymerization was stopped by venting of propylene following injection of ethanol into the reaction medium giving 5.0 g of polypropylene. JC NMR (mmmm 8.9 %, mmmr 12.3 %, rmmr 4.7 %, mmrr I 1.2 %, mmrm+ rmmr 25.6 %, rmrm 10.5 %, rrrr 3.7 %, mrrr 15.9, mrrm 7.1 %), Mw is 952000 g/mol, Mw/Mn is 10.1 . Mechanical properties: elasticity modulus 2.9 MPa, rupture stress >0.6 MPa, elongation at rupture > 1800 %. recovery set after 300 % elongation 6.4 % (Fig. 2, 4).
Example N°5 Propylene polymerization has been carried out in the medium of liquid propylene in stainless steel reactor (200 ml) under rigorous stirring of reaction medium. The 200 ml stainless steel reactor equipped with mechanical stirrer was heated to 70°C for 1.5 hours with continues pumping out the residues of moisture and air then it was cooled to ambient temperature and purged with gaseous propylene with following filling with 50 ml of liquid propylene. The reactor was heated to 50°C maintaining pressure of 40 atm and 1 ,35 ml of 10% solution of MAO (10.35 mmol) (AlMAθ/Ti=300
mol/mol) was introduced into reaction medium, in toluene was injected. Then glass ampoule containing 4,128 mg (2.3 μmol) of bis[4,4'-bis-(3,5-di-tert-butylsaIicylidene) perfluorodiphenile]titanium(IV) dichloride was injected into reactor with following braking with special plunger. In 1.5 hour the polymerization was stopped by venting of propylene following injection of ethanol into the reaction medium giving 6.9 g of polypropylene Microstructure of PP sample is close to that of atactic polypropylene.
I3C NMR (mmmm 8.9 %, mmmr 12.3 %, rmmr 4.7 %, mmrr 1 1.2 %, mmrm+ rmmr 25.6 %, rmrm
10.5 %, rrrr 3.7 %, mrrr 15.9, mrrm 7.1 %), Mw is 9872000 g/mol, Mw/Mn is 8.8. Physico mechanical properties of PP sample: elasticity modulus 4.3 MPa, rupture stress >0.8 MPa, elongation at rupture > 1800 %, recovery set after 300 % elongation 6.7 % (Fig.3).
The present invention also can be illustrated hereinafter in more detail with following figures.
En ample A ample ->
Fig.l . Tensile strength measurements on two polymers prepared according to the invention (Example 4 and Example 5) in comparison with polymers have been described in the prior art EP 0 707 016 A1.
Claims
1. A catalyst combination for preparing linear isotactic polymers, said catalyst combination containing a transition metal compound of general Formula I
M - metal of the Fourth Auxiliary Group of the Periodic System, preferably titanium, zirconium, hafnium, vanadium, niobium or tantalum; X1 - halogen or a Ci - C3 liner or branched alkyl, aryl or benzyl X2 - halogen or a d - C3 liner or branched alkyl, aryl or benzyl R1 - H or halogen or a linear or branched - C4 alkyl, R2 - H or halogen or a linear or branched C\ - C4 alkyl, R3 - H or halogen or a linear or branched - C4 alkyl, R4 - H or halogen or a linear or branched - C alkyl, and an activator.
2. A catalyst combination as well as an activator according to claim 1, wherein the activator is an open-chain or cyclic alumoxane compound of general Formula II or III
wherein R7 is a Ci - C alkyl group and n is a number between 5 and 30, and/or a cationic activator of genera Formulas VI to VIII B(C6F5)3 (VI) R8 3C[B(C5F5)4] (VII)
[R8 3NH][B(C6F5)4] (VIII)
17 wherein R8 is a C\ to C4 alkyl, or an aryl group.
3. A catalyst combination according to Claims 1 to 2, wherein the transition metal compound of general Formula I and an activator according to general Formulas II to VI are used in such quantities that the atomic ratio between aluminum from the alumoxane and/or boron from the cationic activator and the transition metal from the transition metal compound is within the range of from 1 : 1 to 106:1.
4. A process for preparing polymers and copolymers from a C2 to C2o olefin, or a C5 - C2o cycloolefin or combinations of two or several from those mentioned above as monomer in which process a C2 to C2o olefin, or a C5 - C2o cycloolefin or combinations of two or several from those mentioned are reacted with a catalyst combination being defined in claim 1 to 3.
5. A process according to Cairn 4, wherein the polymerization reaction is carried out in the gas phase, in suspension or in liquid or supercritical monomers, especially in solvents inert under the polymerization conditions.
6. A process according to claim 5 or 6, wherein the inert solvent used herein is any from the listed or mixture of several from listed: benzene, toluene, xylene, ethylbenzene, propane, n-butane, i- butane, pentane, hexane, heptane, any organic liquid which do not contain reactive moieties.
7. A process according to at least one of Claims 4 to 6 where the polymerization is carried out at pressures of from 1 to 100 bars, preferably from 3 to 20 bars and more preferably from 5 to 15 bars, and at temperatures of from - 50 to 200 °C, of preference from 10 to 150 °C and especially at from 20 to 40 °C.
8. Linear, thermoplastic, elastic polymers from at least one from C2 to C2υ olefin, or a C5 - C2o cycloolefin or combinations of two or several herein mentioned with an isotactic arrangement of the monomer units and a statistic distribution of stereoscopic errors along the polymeric chains having isotacticity being within the range of from 15 to 75% of [mmmm] pentad concentration, and a weight average molecular weight Mw of the polymers within the range of from 300,000 to 4,000,000 gms/mol, more preferably within the range from 1,000,000 to 2,000,000, polydispersity within the range from 1.4 to 12 and polymodal, or preferably monomodal Gauss like type molecular weight distribution prepared with the use of catalyst combination and the process according to the Claim 1-6.
15 
Fig. 4. The fragment of the 13C NMR spectrum of polypropylene according to the invention accompanied with computer simulation of signals demonstrating the presence of stereoerrors and absence of regioerrors.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2235068A1 (en) * | 2008-01-14 | 2010-10-06 | Agency for Science, Technology And Research | Self-assembled olefin polymerization catalyst |
| US8420563B2 (en) | 2007-03-29 | 2013-04-16 | Saudi Basic Industries Corporation | Catalyst complex and process for producing multimodal molecular weight polyolefins |
| US20130137841A1 (en) * | 2010-03-25 | 2013-05-30 | He Kuan Luo | Self-assembled multi-nuclear catalyst for olefin polymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5594080A (en) * | 1994-03-24 | 1997-01-14 | Leland Stanford, Jr. University | Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor |
| EP0874005A1 (en) * | 1997-04-25 | 1998-10-28 | Mitsui Chemicals, Inc. | Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and Alpha-olefin/conjugated diene copolymers |
-
2004
- 2004-04-09 WO PCT/RU2004/000134 patent/WO2005097837A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5594080A (en) * | 1994-03-24 | 1997-01-14 | Leland Stanford, Jr. University | Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor |
| EP0874005A1 (en) * | 1997-04-25 | 1998-10-28 | Mitsui Chemicals, Inc. | Olefin polymerization catalysts, transition metal compounds, processes for olefin polymerization, and Alpha-olefin/conjugated diene copolymers |
Non-Patent Citations (1)
| Title |
|---|
| STRACUH J. ET AL.: "Formation and structural properties of salicylaldiminato complexes of zirconium and titanium.", ORGANISCH-CHEMISCHES INSTITUT DER UNIVERSITAT MUNSTER., 17 December 2003 (2003-12-17) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8420563B2 (en) | 2007-03-29 | 2013-04-16 | Saudi Basic Industries Corporation | Catalyst complex and process for producing multimodal molecular weight polyolefins |
| EP2235068A1 (en) * | 2008-01-14 | 2010-10-06 | Agency for Science, Technology And Research | Self-assembled olefin polymerization catalyst |
| US20110124831A1 (en) * | 2008-01-14 | 2011-05-26 | Agency For Science, Technology And Research | Self-assembled olefin polymerization catalyst |
| EP2235068A4 (en) * | 2008-01-14 | 2011-11-30 | Agency Science Tech & Res | SELF-ASSEMBLED CATALYST OF OLEFIN POLYMERIZATION |
| US20130137841A1 (en) * | 2010-03-25 | 2013-05-30 | He Kuan Luo | Self-assembled multi-nuclear catalyst for olefin polymerization |
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