CA1074047A - Process for polymerizing alkenes-1 - Google Patents
Process for polymerizing alkenes-1Info
- Publication number
- CA1074047A CA1074047A CA258,630A CA258630A CA1074047A CA 1074047 A CA1074047 A CA 1074047A CA 258630 A CA258630 A CA 258630A CA 1074047 A CA1074047 A CA 1074047A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- halide
- ester
- compound
- magnesium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 6
- 150000002148 esters Chemical class 0.000 claims abstract description 38
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- 239000010936 titanium Substances 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 22
- -1 titanium halide Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 150000004796 dialkyl magnesium compounds Chemical class 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002879 Lewis base Substances 0.000 claims description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 150000007527 lewis bases Chemical class 0.000 claims description 10
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 0.000 claims description 5
- 238000002083 X-ray spectrum Methods 0.000 claims description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 3
- 229960002337 magnesium chloride Drugs 0.000 claims 2
- 235000011147 magnesium chloride Nutrition 0.000 claims 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005977 Ethylene Substances 0.000 abstract 1
- 125000005234 alkyl aluminium group Chemical group 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 125000002370 organoaluminium group Chemical group 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 4
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910010066 TiC14 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- HJHVQCXHVMGZNC-JCJNLNMISA-M sodium;(2z)-2-[(3r,4s,5s,8s,9s,10s,11r,13r,14s,16s)-16-acetyloxy-3,11-dihydroxy-4,8,10,14-tetramethyl-2,3,4,5,6,7,9,11,12,13,15,16-dodecahydro-1h-cyclopenta[a]phenanthren-17-ylidene]-6-methylhept-5-enoate Chemical compound [Na+].O[C@@H]([C@@H]12)C[C@H]3\C(=C(/CCC=C(C)C)C([O-])=O)[C@@H](OC(C)=O)C[C@]3(C)[C@@]2(C)CC[C@@H]2[C@]1(C)CC[C@@H](O)[C@H]2C HJHVQCXHVMGZNC-JCJNLNMISA-M 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZKSADANYBSWZAB-UHFFFAOYSA-N CCCCCC[Mg]CCCCCC Chemical compound CCCCCC[Mg]CCCCCC ZKSADANYBSWZAB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010061 TiC13 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010386 TiI4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- QQHRHLXGCZWTDK-UHFFFAOYSA-L butylaluminum(2+);dibromide Chemical compound [Br-].[Br-].CCCC[Al+2] QQHRHLXGCZWTDK-UHFFFAOYSA-L 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- FLFGMNFGOKXUQY-UHFFFAOYSA-L dichloro(propan-2-yl)alumane Chemical compound [Cl-].[Cl-].CC(C)[Al+2] FLFGMNFGOKXUQY-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- KMYFNYFIPIGQQZ-UHFFFAOYSA-N magnesium;octane Chemical compound [Mg+2].CCCCCCC[CH2-].CCCCCCC[CH2-] KMYFNYFIPIGQQZ-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- RBLGTYCOUOIUNY-UHFFFAOYSA-L octylaluminum(2+);dichloride Chemical compound CCCCCCCC[Al](Cl)Cl RBLGTYCOUOIUNY-UHFFFAOYSA-L 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl 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])C([H])([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 1
- 239000002245 particle Substances 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl 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])C([H])([H])C([H])([H])C([H])([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 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000012721 stereospecific polymerization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 229940086542 triethylamine Drugs 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
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- DFLYRVOWPYSYMZ-UHFFFAOYSA-N tris(3-methylbut-2-enyl)alumane Chemical compound CC(C)=CC[Al](CC=C(C)C)CC=C(C)C DFLYRVOWPYSYMZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT
Process for polymerizing an alkene-1, ethylene or mixtures thereof by employing a catalyst which comprises (1) a titanium component which is a titanium halide supported on a magnesium-dihalide or manganese-dihalide support and (2) an organoaluminum component which comprises (a) a complex of an aluminum trialkyl and an ester of a carboxylic acid and an alcohol and (b) the reaction product of a dialkyl magnesium compound and an alkyl-aluminum dihalide, which results in a polymer of high stereospecificity.
Process for polymerizing an alkene-1, ethylene or mixtures thereof by employing a catalyst which comprises (1) a titanium component which is a titanium halide supported on a magnesium-dihalide or manganese-dihalide support and (2) an organoaluminum component which comprises (a) a complex of an aluminum trialkyl and an ester of a carboxylic acid and an alcohol and (b) the reaction product of a dialkyl magnesium compound and an alkyl-aluminum dihalide, which results in a polymer of high stereospecificity.
Description
This invention relates to a process for polymerizing ~-alkenes to form homopolymers or copolymers in the presence of a polymerization catalyst comlrising a titanium-halide component supported on a water-free magnesium halide or manganese-halide carrier, and an organoaluminum component; and particularly relates to such polymerization processes having an improved organo-aluminum component. The invention also provides shaped articles of polymers thus prepared.
A known catalyst system includes a titanium-halide component con-sisting of a titanium halide on a specially activated, water-free magnesium-halide or manganese-halide carrier, the organoaluminum component being the product of an addition reaction between a trialkyl-aluminUm compound and an ester of an organic acid containing oxygen, and is usually a mixture of a complex of the trialkyl-aluminium compound with the said ester and a free trialkyl-aluminUm compound. A catalyst system of this type is particularly useful in the polymerization of propene, butene-l, 4-methyl pentene-l and other a-alkenes. However the stereospecificity of the polymer product with such a catalyst leaves much to be desired.
The invention provides for the use of a catalyst system of the type hereinbefore referred to, which when used for polymerizing a-alkenes shows a particularly high activity together with a very high stereospecifi-city. Another advantage is that a polymer product is obtained having a large average particle size, which is advantageous when processing the pro-duct to powder.
The invention provides a process for polymerizing an ~-alkene in the presence of a catalyst system comprising a titanium-halide component sup-ported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminum component that contains ~a) a complex of a trialkyl-aluminum compound with an ester of a carboxylic acid, and ~b) the reaction product of a dialkyl-magnesium compound and a monoalkyl-aluminùm dihalide.
, ~ ', :107~047 Th~ organo-aluminium component is preferably free of nol~-complexed trialkyl-aluminium compound~ as the presence of non-complexed trialkyl-aluminium compound detracts from the stereospecificity of the catalyst system.
The process according to the in~ention is used in particular in the stereospecific polymerization of C~-C~ oralkenes, e g. propene, butene-1, 4-methyl pentene-l and hexene, and in the copolymerization of such ~-alkenes with each other and/or with ethene. Copolymers with a random distribution of the various monomer units and block copolymers, may be thus prepared.
If ethene is used as comonomer it is usually incorporated in a minor propor-tion e.g. up to 30 %, more particularly between 1 % and 15 ~ by weight, based on the said ~-alkene.
The titanium halide is present in the titanium halide component on a water-free magnesium halide or manganese-halide carrier. The titanium compound used may be any halogenated compound of divalent, trivalent or tetravalent titanium, including compounds in which part of the titanium valences is utilized for compounds other than those with halogen atoms.
The halogen is preferably bromine, iodine and particularly chlorine. Specific examples of such titanium compounds are TiC13, TiC13.1/3 AlC13, TiC14, Ti~r4, TiI4 and Ti(isobutoxy)2C12.
The titanium halide is preferably present as a complex with a Lewis base. The preferred Lewis base is an ester of a carboxylic acid, more particularly esters of aromatic carboxylic acids e.g. ethyl benzoate, ethyl-p-methoxy-benzoate, n-butyl benzoate, methyl toluate, and dimethyl phthalate. Other examples of suitable esters are esters of saturated aliphatic carboxylic acids, e.g. ethyl acetate, amyl propionate and methyl butyrate, and esters of unsaturated aliphatic carboxylic acids, e.g.
methyl methacrylate, ethyl acrylate, and dimethyl maleinate. The acid component of the ester usually contains from 1 to 9 carbon atoms per molecule or is a natural fatty acid, while the alcohol component of the ester usually contains from 1 to 6 carbon atoms per molecule. Other examples of suitable Lewis bases are triethyl amine, pyridine, ethylene diamine, nitrobenzene and diethylether.
.
' The titanium halide-Lewis base complexes can be obtained in any known way, e.g. by putting together the components of the complex.
The carrier material used may be any water-Eree magnesium halide or manganese halide, but in practice the ctlloride, particularly magnesium chloride, is pre~erred.
Suitable water-free magnesium chloride can be prepared in known manner by dehydration of MgC12.6 H~0.
Particularly good activity and stereospecificity are obtained in the process of the invention using water-free magnesium halide or manganese halide which has a surface area larger than 3 m /g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-acti-vated halide, and which has been activated, for instance as described in the British Patent specification 1387890. Very favourable results are obtained using a water-free magnesium dihalide that has been prepared by making a dialkyl-magnesium compound react with an anhydrous hydrogen halide in a suitable solvent, e.g. n-heptane or another liquid hydrocarbon.
The titanium halide may be put on the carrier for example by simple admixture, preferably by grinding the mixture. If a titanium halide-Lewis base complex is used, it is possible first to form the complex and then to apply it to the carrier, or first to put the urcomplexed titanium halide on the carrier and then to add the Lewis base, either before or after the addition of the organoaluminium component. The titanium content of the ready titanium halide component on the carrier is preferably from-0.1 ~ to 10 % by weight. The Lewis base is present in the titanium halide component in an amount of e.g. C-5 molecules per titanium atom.
The organoaluminium component comprises a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid. Suitable esters are the same esters as used in the titanium-halide component, preferably esters oi aromatic carboxylic acids e.g. as hereinbefore des-cribed. Particularly suitable trialkyl-aluminium compounds are triethyl aluminium, tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium~ trihexyl aluminium and trioctyl aluminium. The Al/Ti ratio is preferably between 10 and 1000 and the molecule-atom ratio of the total amount of bound Lewis base in the catalyst to Ti is preferably between 5 and 500.
As hereinbefore described, l;he organoaluminium compound is pre-B 5 ferably free of uncomplexed trialkyl-aluminium compound, and thus ~_pre-ferably a stoichiometric amount of ester with respect to the trialkyl-aluminium compound is used, apart from the amount of ester used as a con-stituent of the titanium-halide component in some instances.
The exact stoichiometric amount of ester with respect to the tri-alkyl-aluminium compound can be determined by means of microwave titration of the trialkyl-aluminium compound with the ester in the way described in Analytical Chemistry 37 (1965), pp. 229-233.
The microwave titration is carried out by observing the change in transmission of microwaves in a resonance cavity during the course of the reaction of the trialkyl-aluminium compound with the ester. The mea-sured energy loss is the sum of the individual losses of the components present in the resonance cavity. One of these components is made up of the new molecules thereby formed. By plotting the transmission potential ~ , which is defined as:
j 20 a =~ V - 1, where VO = initial transmission potenti&l V = transmission potential at the time of measurement, against the concentration or the amount of reagent added, a curve is ob-tained in which the sharp break indicates the composition of the complex.
This titration is particularly suitable for tha determination of the stoichiometry of complexes, in particular, for the determination of the stoichiometric amount of ester with respect to the trialkyl-aluminium com-pound under the conditions of the polymerization reaction according to the invention.
According to T. Mole and B.A. Jeffery, 'Organoaluminium compounds', Elsevier Publ. Co., Amsterdam (1972), p. 302, a trialkylaluminium compound .
: `
-forms a 1 : 1 complex with an ester. It has been found however that by means of microwave titration that under the polymerization conditions used a normal value for the stoichiometric molar amount of ester with _....
respect to the trialkyl-aluminium compound is 1 : l.S. The determined value depends on the level of purity and the concentrations used and may range for example from 1 : 1.0 to 1 : 2.0, in particular from 1 : 1.2 to 1 : 1.6.
It is to be considered surprising that the best combination of activity and stereospecificity can be obtained with the stoichiometric amount of ester with respect to the trialkyl-aluminium compound as determined by the microwave titration, if use is made of an organoaluminium component that also contains the reaction product of a dialkyl-magnesium compound and a monoalkyl dihalide.
The organoaluminium component contains in addition to the complex of trialkyl-aluminium compound and ester, the reaction product of a dialkylmagnesium ¢ompound and a monoalkyl-aluminium dihalide. The alkyl groups of the dialkyl-magnesium compound preferably contain 1-10 carbon atoms per molecule or form a palmityl or stearyl group. Examples of suitable dialkylmagnesium compounds are diethyl magnesium, di-n-butyl magnesium, di-n-hexyl magnesium and di-n-octyl magnesium. The monoalkyl-aluminium dihalide is preferably a chloride or bromide. Ethyl-aluminium dichloride or di-bromide are particularly suitable, but use may also be made of other monoalkyl-aluminium dihalides, preferably with 1-10 carbon atoms in the alkyl group e.g. isopropyl-aluminium dichloride, n-butyl-aluminium dibromide or n-octyl-aluminium dichloride. The reaction product of the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide is preferably added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
The molar ratio between the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide may for example be in the range 0.1 and 1, preferably between 0.3 and 0.6. Too high molar ratios give rise to ~74~47 insufficiently stereospecific catalysts and too low ratios to insufficient catalyst activity.
The conditions under which +he polym3ri~ation reaction by means of the new catalysts is effected are similar to conditions conventionally used.
Thus the reaction may be carried out in the gaseous phase or in the presence of a liquid vehicle, which may be inert or ~t may be a monomer in liquid form.
Examples of suitable vehicles are aliphatic, cycloaliphatic, aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon a-toms, for example propene, butene-l~ butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene and the xylenes.
The polymerization temperature usually is within the range between -80 and 150 C, preferably between ~0 and 100 C. The pressure may for example be between 1 and 30 atmospheres.
If so desired the molecular weight of the polymer may be controlled during the polymerization, e.g. by effecting the polymerization in the presence of hydrogen or another well-known molecular-weight regulator.
To prepare block copolymers, the monomers may be added in any desired order.
The process according to the invention is of particular importance in the preparation of isotactic polypropene, random copolymers of propene with minor amounts of ethene, and block copolymers of propene and ethene.
The following Examples of the invention are provided:
_etermination of the stoichiometrio amount of ester with respect to the trialkyl-aluminium compound 50 ml of water-free gasoline were introduced into a mixing vessel of the apparatus described in Analytical Chemistry 37 (1965), pp. 229-233.
3 ml of a 0.1 M solution of triethyl aluminium in gasoline were than added.
The titration was carried out with a 0.1 M solution of ethyl benzoate in water-free ga~ollne. The scale of the millivolt recorder was set to 20 mV
~n / 0~ V~ D f ~ 30 The ~-value is plotted against the number of ~ ~ 5~.v~
; ethyl benzoate added (n), the break indicating the equivalence point, as shown in the graph of the accompanying drawing. The ~ -value is defined as `` 1~74~:)47 , where V denotes the initial transmission potential and V the transmission potential at the time of measurement.
_ample I
6.5 ml of water-free ethyl ben~oate dissolved in 75 ml of water-free gasoline were added at 0 C to a solution of 5 ml of TiCl4 in 125 ml of gasoline that had been flushed with dry nitrogen, and the resulting complex TiC14.C6H5COOC2H5 precipitated This precipitate was filtered, washed and dried in a water-free nitrogen atmosphere.
0.348 g of the complex TiC14.C6H5COOC2H5 and 4.166 g of water-free magnesium chloride thus obtained were ground together in an agate ball mill for 16 hours in a nitrogen atmosphere. 0.448 g (containing 0.102 mmole of titanium) of the ground mixture was suspended in a solution consisting of 1.23 ml of triethyl aluminium and 0.86 ml of ethyl ben~oate in 50 ml of water-free gasoline and prepared under nitrogen and at room temperature five minutes before (this solution contained amounts of triethyl aluminium and ethyl benzoate corresponding to the stoichiometry determined by the micro-wave titration).
1.8 litre of water-free gasoline were introduced into a stainless-steel 3-litre autoclave equipped with a mechanical stirrer and having previsously been flushed with dry nitrogen. 4.5 ml of a solution of gasoline and the reaction product of 9 mmoles of di-n-butyl magnesium and 18 mmoles of ethyl-aluminium di-chloride were then added, after which the suspension thus obtained was added to the reaction system. The temperature of the autoclave was raised to 65 C and propene introduced therein with vigorous stirring. The propene pressure was controlled at 3 atmospheres durlng the polymerization. After 1 hour the reaction was stopped and the white powdery product filtered off.
The yield of polypropene was 59,000 g per g of titanium compound used (calculated as titanium). The content of isotactic material that is 30 not soluble in gasoline of 65 C was 96.2 % by weight. 50 % by weight of the polymer parti¢les had a diameter of over 220 ~ m. -Example II
The procedure of Example I was followed, except that only 3 mmoles of di-n-butyl magnesium and 6 mmoles of ethyl-aluminium dichloride were used, instead of 9 and 18 mmoles, respectively.
The yield of polypropene was 31,2~0 g per g of ti-tanium used.
The content of isotactic material that is not soluble in gasoline of 65 C
was 96.6 % by weight.
Comparative Experiments The following comparative experiments were carried out in a way analogous to that described in Example I, except for the alterations speci-fied in the accompanying ~ ; wherein DBM denotes di-n-butyl magnesium;
MEAC denotes tmono)ethyl-aluminium dichloride and TEA denotes triethyl aluminium.
Exp. molar amount of amount of yield g isotactic ) molar TEA/ethyl Al/Ti DBM mmoles ~ mmoles per g of % by w. benzoate ratio ratio ~ titanium A 180 0 0 41,500 87.4 3.4 B 76 0 0 11,500 92.4 1.5 ) C 76 9 0 13,900 65.4 1.52) 1) insoluble in gasoline of 65 C
A known catalyst system includes a titanium-halide component con-sisting of a titanium halide on a specially activated, water-free magnesium-halide or manganese-halide carrier, the organoaluminum component being the product of an addition reaction between a trialkyl-aluminUm compound and an ester of an organic acid containing oxygen, and is usually a mixture of a complex of the trialkyl-aluminium compound with the said ester and a free trialkyl-aluminUm compound. A catalyst system of this type is particularly useful in the polymerization of propene, butene-l, 4-methyl pentene-l and other a-alkenes. However the stereospecificity of the polymer product with such a catalyst leaves much to be desired.
The invention provides for the use of a catalyst system of the type hereinbefore referred to, which when used for polymerizing a-alkenes shows a particularly high activity together with a very high stereospecifi-city. Another advantage is that a polymer product is obtained having a large average particle size, which is advantageous when processing the pro-duct to powder.
The invention provides a process for polymerizing an ~-alkene in the presence of a catalyst system comprising a titanium-halide component sup-ported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminum component that contains ~a) a complex of a trialkyl-aluminum compound with an ester of a carboxylic acid, and ~b) the reaction product of a dialkyl-magnesium compound and a monoalkyl-aluminùm dihalide.
, ~ ', :107~047 Th~ organo-aluminium component is preferably free of nol~-complexed trialkyl-aluminium compound~ as the presence of non-complexed trialkyl-aluminium compound detracts from the stereospecificity of the catalyst system.
The process according to the in~ention is used in particular in the stereospecific polymerization of C~-C~ oralkenes, e g. propene, butene-1, 4-methyl pentene-l and hexene, and in the copolymerization of such ~-alkenes with each other and/or with ethene. Copolymers with a random distribution of the various monomer units and block copolymers, may be thus prepared.
If ethene is used as comonomer it is usually incorporated in a minor propor-tion e.g. up to 30 %, more particularly between 1 % and 15 ~ by weight, based on the said ~-alkene.
The titanium halide is present in the titanium halide component on a water-free magnesium halide or manganese-halide carrier. The titanium compound used may be any halogenated compound of divalent, trivalent or tetravalent titanium, including compounds in which part of the titanium valences is utilized for compounds other than those with halogen atoms.
The halogen is preferably bromine, iodine and particularly chlorine. Specific examples of such titanium compounds are TiC13, TiC13.1/3 AlC13, TiC14, Ti~r4, TiI4 and Ti(isobutoxy)2C12.
The titanium halide is preferably present as a complex with a Lewis base. The preferred Lewis base is an ester of a carboxylic acid, more particularly esters of aromatic carboxylic acids e.g. ethyl benzoate, ethyl-p-methoxy-benzoate, n-butyl benzoate, methyl toluate, and dimethyl phthalate. Other examples of suitable esters are esters of saturated aliphatic carboxylic acids, e.g. ethyl acetate, amyl propionate and methyl butyrate, and esters of unsaturated aliphatic carboxylic acids, e.g.
methyl methacrylate, ethyl acrylate, and dimethyl maleinate. The acid component of the ester usually contains from 1 to 9 carbon atoms per molecule or is a natural fatty acid, while the alcohol component of the ester usually contains from 1 to 6 carbon atoms per molecule. Other examples of suitable Lewis bases are triethyl amine, pyridine, ethylene diamine, nitrobenzene and diethylether.
.
' The titanium halide-Lewis base complexes can be obtained in any known way, e.g. by putting together the components of the complex.
The carrier material used may be any water-Eree magnesium halide or manganese halide, but in practice the ctlloride, particularly magnesium chloride, is pre~erred.
Suitable water-free magnesium chloride can be prepared in known manner by dehydration of MgC12.6 H~0.
Particularly good activity and stereospecificity are obtained in the process of the invention using water-free magnesium halide or manganese halide which has a surface area larger than 3 m /g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-acti-vated halide, and which has been activated, for instance as described in the British Patent specification 1387890. Very favourable results are obtained using a water-free magnesium dihalide that has been prepared by making a dialkyl-magnesium compound react with an anhydrous hydrogen halide in a suitable solvent, e.g. n-heptane or another liquid hydrocarbon.
The titanium halide may be put on the carrier for example by simple admixture, preferably by grinding the mixture. If a titanium halide-Lewis base complex is used, it is possible first to form the complex and then to apply it to the carrier, or first to put the urcomplexed titanium halide on the carrier and then to add the Lewis base, either before or after the addition of the organoaluminium component. The titanium content of the ready titanium halide component on the carrier is preferably from-0.1 ~ to 10 % by weight. The Lewis base is present in the titanium halide component in an amount of e.g. C-5 molecules per titanium atom.
The organoaluminium component comprises a complex of a trialkyl-aluminium compound with an ester of a carboxylic acid. Suitable esters are the same esters as used in the titanium-halide component, preferably esters oi aromatic carboxylic acids e.g. as hereinbefore des-cribed. Particularly suitable trialkyl-aluminium compounds are triethyl aluminium, tripropyl aluminium, triisobutyl aluminium, triisoprenyl aluminium~ trihexyl aluminium and trioctyl aluminium. The Al/Ti ratio is preferably between 10 and 1000 and the molecule-atom ratio of the total amount of bound Lewis base in the catalyst to Ti is preferably between 5 and 500.
As hereinbefore described, l;he organoaluminium compound is pre-B 5 ferably free of uncomplexed trialkyl-aluminium compound, and thus ~_pre-ferably a stoichiometric amount of ester with respect to the trialkyl-aluminium compound is used, apart from the amount of ester used as a con-stituent of the titanium-halide component in some instances.
The exact stoichiometric amount of ester with respect to the tri-alkyl-aluminium compound can be determined by means of microwave titration of the trialkyl-aluminium compound with the ester in the way described in Analytical Chemistry 37 (1965), pp. 229-233.
The microwave titration is carried out by observing the change in transmission of microwaves in a resonance cavity during the course of the reaction of the trialkyl-aluminium compound with the ester. The mea-sured energy loss is the sum of the individual losses of the components present in the resonance cavity. One of these components is made up of the new molecules thereby formed. By plotting the transmission potential ~ , which is defined as:
j 20 a =~ V - 1, where VO = initial transmission potenti&l V = transmission potential at the time of measurement, against the concentration or the amount of reagent added, a curve is ob-tained in which the sharp break indicates the composition of the complex.
This titration is particularly suitable for tha determination of the stoichiometry of complexes, in particular, for the determination of the stoichiometric amount of ester with respect to the trialkyl-aluminium com-pound under the conditions of the polymerization reaction according to the invention.
According to T. Mole and B.A. Jeffery, 'Organoaluminium compounds', Elsevier Publ. Co., Amsterdam (1972), p. 302, a trialkylaluminium compound .
: `
-forms a 1 : 1 complex with an ester. It has been found however that by means of microwave titration that under the polymerization conditions used a normal value for the stoichiometric molar amount of ester with _....
respect to the trialkyl-aluminium compound is 1 : l.S. The determined value depends on the level of purity and the concentrations used and may range for example from 1 : 1.0 to 1 : 2.0, in particular from 1 : 1.2 to 1 : 1.6.
It is to be considered surprising that the best combination of activity and stereospecificity can be obtained with the stoichiometric amount of ester with respect to the trialkyl-aluminium compound as determined by the microwave titration, if use is made of an organoaluminium component that also contains the reaction product of a dialkyl-magnesium compound and a monoalkyl dihalide.
The organoaluminium component contains in addition to the complex of trialkyl-aluminium compound and ester, the reaction product of a dialkylmagnesium ¢ompound and a monoalkyl-aluminium dihalide. The alkyl groups of the dialkyl-magnesium compound preferably contain 1-10 carbon atoms per molecule or form a palmityl or stearyl group. Examples of suitable dialkylmagnesium compounds are diethyl magnesium, di-n-butyl magnesium, di-n-hexyl magnesium and di-n-octyl magnesium. The monoalkyl-aluminium dihalide is preferably a chloride or bromide. Ethyl-aluminium dichloride or di-bromide are particularly suitable, but use may also be made of other monoalkyl-aluminium dihalides, preferably with 1-10 carbon atoms in the alkyl group e.g. isopropyl-aluminium dichloride, n-butyl-aluminium dibromide or n-octyl-aluminium dichloride. The reaction product of the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide is preferably added to the reaction product of the titanium-halide component and the complex of the trialkyl-aluminium compound with the ester.
The molar ratio between the dialkyl-magnesium compound and the monoalkyl-aluminium dihalide may for example be in the range 0.1 and 1, preferably between 0.3 and 0.6. Too high molar ratios give rise to ~74~47 insufficiently stereospecific catalysts and too low ratios to insufficient catalyst activity.
The conditions under which +he polym3ri~ation reaction by means of the new catalysts is effected are similar to conditions conventionally used.
Thus the reaction may be carried out in the gaseous phase or in the presence of a liquid vehicle, which may be inert or ~t may be a monomer in liquid form.
Examples of suitable vehicles are aliphatic, cycloaliphatic, aromatic and mixed aromatic/aliphatic hydrocarbons with 3-8 carbon a-toms, for example propene, butene-l~ butane, isobutane, n-hexane, n-heptane, cyclohexane, benzene, toluene and the xylenes.
The polymerization temperature usually is within the range between -80 and 150 C, preferably between ~0 and 100 C. The pressure may for example be between 1 and 30 atmospheres.
If so desired the molecular weight of the polymer may be controlled during the polymerization, e.g. by effecting the polymerization in the presence of hydrogen or another well-known molecular-weight regulator.
To prepare block copolymers, the monomers may be added in any desired order.
The process according to the invention is of particular importance in the preparation of isotactic polypropene, random copolymers of propene with minor amounts of ethene, and block copolymers of propene and ethene.
The following Examples of the invention are provided:
_etermination of the stoichiometrio amount of ester with respect to the trialkyl-aluminium compound 50 ml of water-free gasoline were introduced into a mixing vessel of the apparatus described in Analytical Chemistry 37 (1965), pp. 229-233.
3 ml of a 0.1 M solution of triethyl aluminium in gasoline were than added.
The titration was carried out with a 0.1 M solution of ethyl benzoate in water-free ga~ollne. The scale of the millivolt recorder was set to 20 mV
~n / 0~ V~ D f ~ 30 The ~-value is plotted against the number of ~ ~ 5~.v~
; ethyl benzoate added (n), the break indicating the equivalence point, as shown in the graph of the accompanying drawing. The ~ -value is defined as `` 1~74~:)47 , where V denotes the initial transmission potential and V the transmission potential at the time of measurement.
_ample I
6.5 ml of water-free ethyl ben~oate dissolved in 75 ml of water-free gasoline were added at 0 C to a solution of 5 ml of TiCl4 in 125 ml of gasoline that had been flushed with dry nitrogen, and the resulting complex TiC14.C6H5COOC2H5 precipitated This precipitate was filtered, washed and dried in a water-free nitrogen atmosphere.
0.348 g of the complex TiC14.C6H5COOC2H5 and 4.166 g of water-free magnesium chloride thus obtained were ground together in an agate ball mill for 16 hours in a nitrogen atmosphere. 0.448 g (containing 0.102 mmole of titanium) of the ground mixture was suspended in a solution consisting of 1.23 ml of triethyl aluminium and 0.86 ml of ethyl ben~oate in 50 ml of water-free gasoline and prepared under nitrogen and at room temperature five minutes before (this solution contained amounts of triethyl aluminium and ethyl benzoate corresponding to the stoichiometry determined by the micro-wave titration).
1.8 litre of water-free gasoline were introduced into a stainless-steel 3-litre autoclave equipped with a mechanical stirrer and having previsously been flushed with dry nitrogen. 4.5 ml of a solution of gasoline and the reaction product of 9 mmoles of di-n-butyl magnesium and 18 mmoles of ethyl-aluminium di-chloride were then added, after which the suspension thus obtained was added to the reaction system. The temperature of the autoclave was raised to 65 C and propene introduced therein with vigorous stirring. The propene pressure was controlled at 3 atmospheres durlng the polymerization. After 1 hour the reaction was stopped and the white powdery product filtered off.
The yield of polypropene was 59,000 g per g of titanium compound used (calculated as titanium). The content of isotactic material that is 30 not soluble in gasoline of 65 C was 96.2 % by weight. 50 % by weight of the polymer parti¢les had a diameter of over 220 ~ m. -Example II
The procedure of Example I was followed, except that only 3 mmoles of di-n-butyl magnesium and 6 mmoles of ethyl-aluminium dichloride were used, instead of 9 and 18 mmoles, respectively.
The yield of polypropene was 31,2~0 g per g of ti-tanium used.
The content of isotactic material that is not soluble in gasoline of 65 C
was 96.6 % by weight.
Comparative Experiments The following comparative experiments were carried out in a way analogous to that described in Example I, except for the alterations speci-fied in the accompanying ~ ; wherein DBM denotes di-n-butyl magnesium;
MEAC denotes tmono)ethyl-aluminium dichloride and TEA denotes triethyl aluminium.
Exp. molar amount of amount of yield g isotactic ) molar TEA/ethyl Al/Ti DBM mmoles ~ mmoles per g of % by w. benzoate ratio ratio ~ titanium A 180 0 0 41,500 87.4 3.4 B 76 0 0 11,500 92.4 1.5 ) C 76 9 0 13,900 65.4 1.52) 1) insoluble in gasoline of 65 C
2) stoichiometry determined by microwave titration.
Experiment A shows that a catalyst system that contains non-complexed trialkyl aluminium but no reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide, can provide a high catalyst activity as manifested by the yleld per gram of titanium, but the stereo-specificity of the catalyst is low. Almost 13 % of the propene monomer used was converted into undesired atactic polymer.
In experiment B, the stoichiometric trialkyl-aluminium compound/
ester ratio is used, but the catalyst does not contain any reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide. The activity o$
such a catalyst system is low.
1074~47 If a stoichiometric trialkyl-aluminium compound/ester ratio is us~d, but only dialkyl magnesium is used instead of the reaction product of a dialkyl-magnesium and a mono-alkyl-aluminium dihalide, the stereo-specificity of the catalyst is very poor (Experiment C).
Experiment A shows that a catalyst system that contains non-complexed trialkyl aluminium but no reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide, can provide a high catalyst activity as manifested by the yleld per gram of titanium, but the stereo-specificity of the catalyst is low. Almost 13 % of the propene monomer used was converted into undesired atactic polymer.
In experiment B, the stoichiometric trialkyl-aluminium compound/
ester ratio is used, but the catalyst does not contain any reaction product of a dialkyl-magnesium and a monoalkyl-aluminium dihalide. The activity o$
such a catalyst system is low.
1074~47 If a stoichiometric trialkyl-aluminium compound/ester ratio is us~d, but only dialkyl magnesium is used instead of the reaction product of a dialkyl-magnesium and a mono-alkyl-aluminium dihalide, the stereo-specificity of the catalyst is very poor (Experiment C).
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for polymerizing an .alpha.-alkene in the presence of a cata-lyst system comprising a titanium-halide component supported on a water-free magnesium-halide or manganese-halide carrier, and an organo-aluminum component that contains (a) a complex of a trialkyl-aluminum compound with an ester of a carboxylic acid, and (b) the reaction product of a dialkyl-magnesium compound and a monoalkyl-aluminum dihalide.
2. A process according to claim 1 wherein the organo-aluminum component is free of non-complexed trialkyl-aluminum compound.
3. A process according to claim 1 wherein the titanium-halide component is a complex of a halogenated titanium compound with a Lewis base on a water-free magnesium-chloride carrier.
4. A process according to claim 2 wherein the titanium-halide component is a complex of a halogenated titanium compound with a Lewis base on a water-free magnesium-chloride carrier.
5. A process according to claim 3 wherein the said Lewis base is an ester of a carboxylic acid.
6. A process according to claim 4 wherein the said Lewis base is an ester of a carboxylic acid.
7. A process according to any of claims 1, 2 or 3 wherein the said ester is an ester of an aromatic carboxylic acid.
8. A process according to claim 4 wherein the said ester is an ester of an aromatic carboxylic acid.
9. A process according to any of claims 1, 2 or 3 wherein the said carrier is an activated magnesium-halide or an activated manganese-halide each of which has a surface area larger than 3 m2/g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-activated halide.
10. A process according to claim 8 wherein the said carrier is an activated magnesium-halide or an activated manganese-halide each of which has a surface area larger than 3 m2/g, and/or shows broadened diffraction lines in the X-ray spectrum compared to the normal, non-activated halide.
11. A process according to any of claims 1, 2 or 3 wherein the said reaction product of the dialkyl-magnesium compound with the monoalkyl-aluminum dihalide is added to the reaction product of the titanium halide component and the complex of the trialkyl-aluminum compound with the ester.
12. A process according to claim 10 wherein the said reaction product of the dialkyl-magnesium compound with the monoalkyl-aluminum dihalide is added to the reaction product of the titanium halide component and the complex of the trialkyl-aluminum compound with the ester.
13. A process according to any of claims 1, 2 or 3 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.1 : 1 and 1 : 1.
14. A process according to claim 12 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.1 ? 1 and 1 : 1.
15. A process according to any of claims 1, 2 or 3 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.3 : 1 and 0.6 : 1.
16. A process according to claim 12 wherein the molar ratio of dialkyl-magnesium compound to monoalkyl-aluminum dihalide is between 0.3:1 and 0.6:1.
17. A process according to any of claims 1, 2 or 3 wherein a polymer of a C3-C6 alkene is prepared, optionally with up to 30% by weight of ethene.
18. A process according to claim 14 wherein a polymer of a C3-C6 alkene is prepared, optionally With up to 30% by weight of ethene.
19. A process according to claim 16 wherein a polymer of a C3-C6 alkene is prepared, optionally with up to 30% by weight of ethene.
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| NL7509736A NL7509736A (en) | 1975-08-15 | 1975-08-15 | PROCESS FOR POLYMERIZING ALKINES-1. |
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| AT (1) | AT342863B (en) |
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| CA (1) | CA1074047A (en) |
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| NL (1) | NL7509736A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4000245B2 (en) | 1999-05-25 | 2007-10-31 | 敏男 村上 | Wiper method and apparatus |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT967867B (en) * | 1972-09-26 | 1974-03-11 | Montedison Spa | PROCEDURE FOR THE STEREOSPECIFICATION OF THE ALPHA OLE FINE |
| GB1492618A (en) * | 1974-02-01 | 1977-11-23 | Mitsui Petrochemical Ind | Process for preparing highly stereoregular polyolefins and catalyst used therefor |
-
1975
- 1975-08-15 NL NL7509736A patent/NL7509736A/en not_active Application Discontinuation
-
1976
- 1976-08-05 BE BE169570A patent/BE844900A/en not_active IP Right Cessation
- 1976-08-06 CA CA258,630A patent/CA1074047A/en not_active Expired
- 1976-08-06 GB GB3288776A patent/GB1547886A/en not_active Expired
- 1976-08-11 DE DE19762636193 patent/DE2636193A1/en not_active Ceased
- 1976-08-12 AU AU16806/76A patent/AU502770B2/en not_active Expired
- 1976-08-12 FR FR7624606A patent/FR2320956A1/en active Granted
- 1976-08-12 AT AT600776A patent/AT342863B/en not_active IP Right Cessation
- 1976-08-13 IT IT5089176A patent/IT1066276B/en active
- 1976-08-14 JP JP9740776A patent/JPS5224293A/en active Pending
- 1976-08-14 ES ES450726A patent/ES450726A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| AT342863B (en) | 1978-04-25 |
| GB1547886A (en) | 1979-06-27 |
| JPS5224293A (en) | 1977-02-23 |
| AU502770B2 (en) | 1979-08-09 |
| FR2320956A1 (en) | 1977-03-11 |
| IT1066276B (en) | 1985-03-04 |
| BE844900A (en) | 1977-02-07 |
| NL7509736A (en) | 1977-02-17 |
| ATA600776A (en) | 1977-08-15 |
| ES450726A1 (en) | 1977-09-01 |
| DE2636193A1 (en) | 1977-02-24 |
| FR2320956B1 (en) | 1982-11-19 |
| AU1680676A (en) | 1978-02-16 |
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| Date | Code | Title | Description |
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| MKEX | Expiry |