WO2009083500A1 - Plastic tanks made from random copolymers of propylene and hexene-1 - Google Patents
Plastic tanks made from random copolymers of propylene and hexene-1 Download PDFInfo
- Publication number
- WO2009083500A1 WO2009083500A1 PCT/EP2008/068036 EP2008068036W WO2009083500A1 WO 2009083500 A1 WO2009083500 A1 WO 2009083500A1 EP 2008068036 W EP2008068036 W EP 2008068036W WO 2009083500 A1 WO2009083500 A1 WO 2009083500A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hexene
- propylene
- copolymer
- plastic tank
- copolymers
- Prior art date
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 25
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 title claims abstract description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title description 8
- 229920005604 random copolymer Polymers 0.000 title description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000008096 xylene Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000004611 light stabiliser Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 description 22
- -1 hydrocarbon radical Chemical group 0.000 description 21
- 239000003054 catalyst Substances 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 10
- 150000003254 radicals Chemical class 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 229910003074 TiCl4 Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002530 phenolic antioxidant Substances 0.000 description 4
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 4
- 239000011949 solid catalyst Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 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
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000003386 piperidinyl group Chemical group 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YXHRTMJUSBVGMX-UHFFFAOYSA-N 4-n-butyl-2-n,4-n-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2-n-[6-[(2,2,6,6-tetramethylpiperidin-4-yl)amino]hexyl]-1,3,5-triazine-2,4-diamine Chemical compound N=1C=NC(N(CCCCCCNC2CC(C)(C)NC(C)(C)C2)C2CC(C)(C)NC(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)NC(C)(C)C1 YXHRTMJUSBVGMX-UHFFFAOYSA-N 0.000 description 2
- OWXXKGVQBCBSFJ-UHFFFAOYSA-N 6-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1,3,5-triazin-2-yl]ami Chemical compound N=1C(NCCCN(CCN(CCCNC=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)C=2N=C(N=C(N=2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 OWXXKGVQBCBSFJ-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- HZDHNJUNAXAQNN-UHFFFAOYSA-N [C].N1CCCCC1 Chemical group [C].N1CCCCC1 HZDHNJUNAXAQNN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000000204 (C2-C4) acyl group Chemical group 0.000 description 1
- UWRXMIQVSKQAIJ-UHFFFAOYSA-N 2-n-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]-[2-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]-[3-[[4,6-bis[butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino]-1h-triazin-2-yl]amino]propyl Chemical compound C=1C(N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)=NN(NCCCN(CCN(CCCNN2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N2N=C(C=C(N2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)N(CCCC)C2CC(C)(C)N(C)C(C)(C)C2)NC=1N(CCCC)C1CC(C)(C)N(C)C(C)(C)C1 UWRXMIQVSKQAIJ-UHFFFAOYSA-N 0.000 description 1
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 description 1
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-UHFFFAOYSA-N 0.000 description 1
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 1
- SYQQWGGBOQFINV-FBWHQHKGSA-N 4-[2-[(2s,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-3-oxo-1,2,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-2-yl]ethoxy]-4-oxobutanoic acid Chemical compound C1CC2=CC(=O)[C@H](CCOC(=O)CCC(O)=O)C[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 SYQQWGGBOQFINV-FBWHQHKGSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SCKHCCSZFPSHGR-UHFFFAOYSA-N cyanophos Chemical compound COP(=S)(OC)OC1=CC=C(C#N)C=C1 SCKHCCSZFPSHGR-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- QWVBGCWRHHXMRM-UHFFFAOYSA-N hexadecoxycarbonyloxy hexadecyl carbonate Chemical compound CCCCCCCCCCCCCCCCOC(=O)OOC(=O)OCCCCCCCCCCCCCCCC QWVBGCWRHHXMRM-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D22/00—Producing hollow articles
- B29D22/003—Containers for packaging, storing or transporting, e.g. bottles, jars, cans, barrels, tanks
-
- 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
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/12—Melt flow index or melt flow ratio
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/1397—Single layer [continuous layer]
Definitions
- Plastic tanks made from random copolymers of propylene and hexene-1
- the present invention relates to plastic tanks made from propylene copolymers of propylene and hexene-1.
- plastic tanks it is intended, for example, expansion tanks, water collecting tanks, vertical and horizontal tanks, cone bottom tanks, open top tanks and others.
- tanks in particular expansion tanks for cooling circuits, are designed for resisting to mid-long term temperature and pressure cycles. These particular conditions, especially at temperatures higher than 100 0 C, cause the occurrence of cracks or crazes under stress well below yield strength of the material. Such crazes can propagate and finally cause leakage or break. At higher stress levels, yielding can occur immediately or after some times with or without appearance of crazes.
- the plastic material used for plastic tanks must be endowed with high mechanical properties. Moreover, since the plastic tanks are produced by injection moulding techniques, said plastic material has to combine optimal intrinsic mechanical properties with the suitability to provide homogeneous injection moulded tanks.
- Propylene copolymers comprising propylene and hexene-1 are already known in the art and used in various applications, for example the international application WO 2005/059210 discloses fibres for thermal bonding comprising random copolymers of propylene and hexene-1 showing good balance of mechanical properties, in particular high tenacity and good elongation at break.
- plastic tanks in particular expansion tanks, made from propylene-hexene-1 copolymers able to give optimal performances in terms of high temperature creep resistance , time to rupture and mode of failure.
- plastic tanks in particular expansion tanks, comprising a propylene-hexene-1 copolymer optionally comprising a further recurring unit derived from ⁇ -olef ⁇ ns selected from ethylene and a C5-C10 ⁇ -olef ⁇ n, hexene-1 excluded, having a xylene soluble fraction lower than 5 %wt, preferably lower than 4%wt with respect to the total weight of the copolymer and satisfying the following relation:
- a ⁇ T B wherein A is the MFR (Melt Flow Rate) measured according to the method ISO 1133 (230° C, 5 kg) expressed in g/10min, T m is the melting temperature measured by DSC expressed in 0 C and B is the hexene-1 content expressed in percentage by weight with respect to the total weight of the copolymer and measured by IR spectroscopy.
- MFR Melt Flow Rate
- the ratio A-T m /B has a value higher than 100, more preferably comprised between 110 and 500.
- propylene-hexene-1 copolymers satisfying the above relation are particularly suitable to be used for plastic tanks, in particular expansion tanks, providing tanks with an optimal balance between mechanical properties such as rigidity and mid-long term high temperature creep resistance and particularly suitable to be used for injection moulding techniques.
- Optimal results in terms of mechanical properties at high temperatures can be obtained when the melting temperature of the propylene-hexene-1 copolymers are higher than 145 0 C, preferably higher than 147°C and, the MFR values are comprised between 0.8 and 30 g/10min, preferably from 1 and 25 g/10min, the hexene-1 content ranges from 0.5 to 5%wt, preferably from 0.2 to 4 %wt, more preferably from 0.2 to 3%wt with respect to the total weight of the copolymer.
- the propylene-hexene-1 copolymers according to the present invention show values of Polydispersity Index determined by rheological method described below typically comprised between 1 and 7, preferably between 2 and 6.
- said propylene-hexene-1 copolymers show tensile modulus values comprised between 150 and 220 MPa, preferably between 180 and 210 MPa measured according to the method described below on specimens cut perpendicular to flow.
- Typical values of Izod at 23°C, measured according to ISO 180/1 A method are comprised between 5 and 20 KJ/m 2 , preferably between 8 and 15 KJ/m 2
- the values of Flexural Modulus can range from 1100 to 1700 N/mm 2 , preferably from 1300 to 1500 N/mm 2 .
- the propylene-hexene-1 polymers used in the present invention can be prepared by polymerisation in one or more polymerisation steps. Such polymerisation can be carried out in the presence of Ziegler-Natta catalysts.
- the polymerization stage is carried out in presence of a highly stereospecif ⁇ c heterogeneous Ziegler-Natta catalyst.
- the Ziegler-Natta catalysts suitable for producing the propylene polymer compositions of the invention comprise a solid catalyst component comprising at least one titanium compound having at least one titanium-halogen bond and at least an electron-donor compound (internal donor), both supported on magnesium chloride.
- the Ziegler-Natta catalysts systems further comprise an organo-aluminum compound as essential co-catalyst and optionally an external electron-donor compound. Suitable catalysts systems are described in the European patents EP45977, EP361494, EP728769, EP 1272533 and in the international patent application WO00/63261.
- the solid catalyst component comprises Mg, Ti, halogen and an electron donor selected from esters of phthalic acids disclosed in EP45977 and in particular of either diisobutylphathalate or dihexylphthalate or diethylphthalate and mixtures thereof.
- the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR) n _ y X y , where n is the valence of titanium and y is a number between 1 and n, preferably TiCl 4 , with a magnesium chloride deriving from an adduct of formula MgCl 2 -PROH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.
- the adduct can be suitably prepared in spherical form by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130 0 C). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Examples of spherical adducts prepared according to this procedure are described in US 4,399,054 and US 4,469,648.
- the so obtained adduct can be directly reacted with the Ti compound or it can be previously subjected to thermal controlled dealcoholation (80-130 0 C) so as to obtain an adduct in which the number of moles of alcohol is generally lower than 3, preferably between 0.1 and 2.5.
- the reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCl 4 (generally 0 0 C); the mixture is heated up to 80-130 0 C and kept at this temperature for 0.5-2 hours.
- the treatment with TiCl 4 can be carried out one or more times.
- the internal donor can be added during the treatment with TiCl 4 and the treatment with the electron donor compound can be repeated one or more times.
- the internal donor is used in molar ratio with respect to the MgCl 2 of from 0.01 to 1 preferably from 0.05 to 0.5.
- the preparation of catalyst components in spherical form is described for example in European patent application EP-A-395083 and in the International patent application WO98/44001.
- the solid catalyst components obtained according to the above method contain the titanium compound, expressed as Ti, generally in an amount from 0.5 to 10% by weight. Moreover, they show a surface area (by B.E.T. method) generally between 20 and 500 mVg and preferably between 50 and 400 m 2 /g, and a total porosity (by B.E.T. method) higher than 0.2 cm 3 /g preferably between 0.2 and 0.6 cm 3 /g.
- the porosity (Hg method) due to pores with radius up to lO.OOOA generally ranges from 0.3 to 1.5 cm 3 /g, preferably from 0.45 to 1 cffiVg.
- the organo-aluminum compound is preferably an alkyl-Al selected from the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n- butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum.
- the Al-alkyl compound is generally used in such a quantity that the Al/Ti ratio be from 1 to 1000.
- Preferred external electron-donor compounds include silicon compounds, ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethyl piperidine, ketones and the 1,3-diethers.
- Another class of preferred external donor compounds is that of silicon compounds of formula Ra 5 Rb 6 Si(OR 7 ) c , where a and b are integer from 0 to 2, c is an integer from 1 to 3 and the sum (a+b+c) is 4; R 5 , R 6 , and R 7 , are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms.
- methylcyclohexyldimethoxysilane diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane and
- the propylene-hexene-1 polymers are preferably prepared by using catalysts containing an ester of phthalic acid as inside donor and (cyclopentyl)2Si(OCH3)2 as outside donor.
- the catalysts generally used in the process of the invention are capable of producing polypropylene with a value of xylene insolubility at ambient temperature greater than
- propylene-hexene-1 polymers can be produced by a well-known polymerisation process.
- such polymers are produced by a polymerisation process carried out in a gas-phase polymerization reactor comprising at least two interconnected polymerisation zones.
- the process is carried out in a first and in a second interconnected polymerization zones into which propylene and hexene-1 are fed in the presence of a catalyst system and from which the polymer produced is discharged.
- the growing polymer particles flow upward through one (first) of the said polymerisation zones (riser) under fast fluidisation conditions, leave said riser and enter another (second) polymerisation zone (downcomer) through which they flow downward in a densif ⁇ ed form under the action of gravity, leave said downcomer and are reintroduced into the riser, thus establishing a circulation of polymer between the riser and the downcomer.
- the condition of fast fluidization in the riser is established by feeding a gas mixture comprising the relevant monomers to said riser. It is preferable that the feeding of the gas mixture is effected below the point of reintroduction of the polymer into said riser by the use, where appropriate, of gas distributor means.
- the velocity of transport gas into the riser is higher than the transport velocity under the operating conditions, preferably from 2 to
- the polymer and the gaseous mixture leaving the riser are conveyed to a solid/gas separation zone.
- the solid/gas separation can be effected by using conventional separation means.
- the polymer enters the downcomer.
- the gaseous mixture leaving the separation zone is compressed, cooled and transferred, if appropriate with the addition of make-up monomers and/or molecular weight regulators, to the riser.
- the transfer can be carried out by means of a recycle line for the gaseous mixture.
- control of the polymer circulation between the two polymerisation zones can be carried out by metering the amount of polymer leaving the downcomer using means suitable for controlling the flow of solids, such as mechanical valves.
- the operating parameters are those that are usual in olefin polymerisation process, for example between 50 to 120 0 C.
- the operating pressures can range between 0.5 and 10 MPa, preferably between 1.5 to 6
- one or more inert gases such as nitrogen or an aliphatic hydrocarbon, are maintained in the polymerization zones, in such quantities that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total pressure of the gases.
- the various catalysts are fed up to the riser at any point of the said riser. However, they can also be fed at any point of the downcomer.
- the catalyst can be in any physical state, therefore catalysts in either solid or liquid state can be used.
- the propylene-hexene-1 copolymers of the invention may also be blended with any other additives commonly employed in the art, such as antioxidants, light stabilizers, heat stabilizers, phenolic antioxidants, slip agents such as calcium stearate and any other nucleating agents selected among talc, aromatic carboxylic salts, salts of monocarboxylic or polycarboxylic acids, e.g. sodium benzoate, aluminum tert-butylbenzoate or dicetyl peroxydicarbonate.
- additives commonly employed in the art, such as antioxidants, light stabilizers, heat stabilizers, phenolic antioxidants, slip agents such as calcium stearate and any other nucleating agents selected among talc, aromatic carboxylic salts, salts of monocarboxylic or polycarboxylic acids, e.g. sodium benzoate, aluminum tert-butylbenzoate or dicetyl peroxydicarbonate.
- the propylene-hexene-1 copolymers of the present invention can be addittivated with at least a Hindered Amine Light Stabiliser (HALS) in place of phenolic antioxidants.
- HALS Hindered Amine Light Stabiliser
- the substitution of phenolic antioxidants with specific amount of HALS provide propylene- hexene-1 copolymers which exhibit a better Yellowness Index with respect to those comprising phenolic antioxidants meaning that the plastic tanks comprising the propylene- hexene-1 copolymers addittivated with HALS show reduced discoloration than those comprising the propylene-hexene-1 copolymers blended with usual packing of stabilisers.
- the HALS used according to the present invention are monomeric or oligomeric compounds containing, in the molecule, one or more substituted piperidine groups having general formula:
- the R29 radicals, equal or different are C1-C4 alkyl radicals, or tetramethylpiperidine radicals, or the alkyl radicals form with the piperidine carbon atoms to which they are linked a C5-C9 cycloalkyl radical;
- the R30 radicals, equal or different, are hydrogen or Ci -C is alkyl radicals, C7-C18 arylalkyl radicals, or the alkyl radical forms with the piperidine carbon atoms to which they are linked a C5-C10 cycloalkyl radical;
- the R31 radicals, equal or different are hydrogen, or C 1 -C 18 alkyl radicals or C7-C18 arylalkyl radicals;
- the R32 radical is hydrogen, or a Ci-Cs alkyl radical, or a benzyl radical;
- Z is hydrogen, or a C 1 -C 18 alkyl, C 1 -C 12 alkylene, C3-C12 alkeny
- Z is a C 1 -C 12 alkyl radical, or a C3-C8 alkenyl, C 7 -C 11 aralkyl radical, or a bivalent radical containing one or more ester groups, being the valences of said radicals linked to the nitrogen atom of piperidine groups.
- HALS include poly[[6- [(l,l,3,3-tetramethylbutyl)amino]-l,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl) imino]- 1 ,6-hexanediy[(2,2,6,6-tetramethy-4-piperidinyl)imino]]; N,N',N",N'"-tetrakis(4,6- bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidin-4-yl)-amino)triazin-2-yl)-4,7-diazadecane- 1,10-diamine; (1,6-hexanediamine, N, N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-polymer, and poly-(N- ⁇ -hydroxyethyl-2,2,6,
- the amount of HALS comprised in the propylene-hexene-1 copolymers according to the present invention can range from 200 to 3000 ppm, preferably from 500 to 2500 ppm.
- PI Polydispersity Index
- specimens for both static and creep tests were cut from injection molded plaques (250x150x3.15mm), some specimens were cut parallel to the direction of the injection flow, some others perpendicular to the direction of the injection flow. Shape of specimen was chosen same as profile of the ISO R527 type IB tensile bars, and thickness was kept the same as the plaques from which specimens were cut (3.15 mm).
- Propylene-hexene-1 polymers are prepared by polymerising propylene and hexene-1 in the presence of a catalyst under continuous conditions in a plant comprising a precontact section, a prepolymerisation section and a polymerisation apparatus that comprises two interconnected cylindrical reactors, riser and downcomer. Fast fluidisation conditions are established in the riser by feeding gas recycled from the gas-solid separator.
- the catalyst employed comprises a catalyst component prepared by analogy with example 5 of EP-A-728769 but using microspheroidal MgCl 2 - 1.7C 2 H 5 OH instead of
- Such catalyst component is mixed with dicyclopentyl dimethoxy silane
- DCPMS DCPMS
- TEAL triethylaluminium
- the catalyst system is then subjected to pre-polymerisation before introducing it into the polymerisation apparatus.
- the polymer particles exiting the reactor are subjected to a steam treatment to remove the reactive monomers and volatile substances and then dried.
- the polymer particles are extruded with a usual packing of stabilisers.
- Said usual packing of stabilizers comprises: 0.1%wt of Calcium Stearate, 0.25%wt of Irgafos
- Example 1 is repeated except that the usual packing of stabilizers was substituted by 0.05%wt of Calcium Stearate and 0.15%wt of Irganox 168 and 0.2%wt of Chimassorb 2020.
- the properties of the propylene-hexene-1 copolymers are reported in Table 2.
- Creep test results in terms of test conditions, failure mode and time, if the specimen failed within the test duration, are reported in Tables 4 and 5 respectively corresponding to the data collected for the specimens cut perpendicular to flow and for the specimens cut parallel to flow. Table 1
- Table 2 Table 3 : Static tensile test results Tab 5 : Creep to rupture test, specimens cut parallel to flow
- the propylene-hexene-1 copolymers according to the present invention show better results in terms of high temperature creep resistance with respect to the propylene- ethylene copolymers of the comparative examples.
- the specimens cut perpendicular to flow show no rupture nor yielding at 130 0 C and 3.5 MPa whereas the propylene-ethylene copolymers according to the comparative examples at the same conditions exhibit poorer long term resistance performances.
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- Engineering & Computer Science (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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US12/735,277 US8252399B2 (en) | 2007-12-28 | 2008-12-19 | Plastic tanks made from random copolymers of propylene and hexene-1 |
RU2010131623/04A RU2474590C2 (en) | 2007-12-28 | 2008-12-19 | Plastic tanks made from random copolymers of propylene and hexene-1 |
CN2008801224943A CN101910219B (en) | 2007-12-28 | 2008-12-19 | Plastic tanks made from random copolymers of propylene and hexene-1 |
EP08867740A EP2235075B1 (en) | 2007-12-28 | 2008-12-19 | Plastic tanks made from random copolymers of propylene and hexene-1 |
JP2010540109A JP2011507773A (en) | 2007-12-28 | 2008-12-19 | Plastic tanks made from random copolymers of propylene and hexene-1 |
BRPI0821806-4A BRPI0821806B1 (en) | 2007-12-28 | 2008-12-19 | PLASTIC TANKS MADE OF RANDOM PROPILENE AND HEXEN-1 COPOLYMERS |
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EP07150453.4 | 2007-12-28 | ||
EP07150453 | 2007-12-28 | ||
US1053408P | 2008-01-09 | 2008-01-09 | |
US61/010,534 | 2008-01-09 |
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PCT/EP2008/068036 WO2009083500A1 (en) | 2007-12-28 | 2008-12-19 | Plastic tanks made from random copolymers of propylene and hexene-1 |
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US (1) | US8252399B2 (en) |
EP (1) | EP2235075B1 (en) |
JP (1) | JP2011507773A (en) |
KR (1) | KR20100113061A (en) |
CN (1) | CN101910219B (en) |
BR (1) | BRPI0821806B1 (en) |
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Cited By (3)
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WO2015062787A1 (en) | 2013-10-30 | 2015-05-07 | Basell Poliolefine Italia S.R.L. | Multimodal copolymers of propylene and 1-hexene |
EP3325553B1 (en) | 2015-07-21 | 2020-10-07 | SABIC Global Technologies B.V. | Expansion reservoir of polypropylene with glass fibers |
EP3766652A1 (en) | 2019-07-16 | 2021-01-20 | Basell Poliolefine Italia S.r.l. | Injection molded container for microwave |
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RU2010131623A (en) | 2012-02-10 |
CN101910219B (en) | 2012-11-21 |
EP2235075B1 (en) | 2012-08-08 |
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RU2474590C2 (en) | 2013-02-10 |
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EP2235075A1 (en) | 2010-10-06 |
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