NO148292B - PROCEDURE FOR POLYMERIZATION OF OLEFINES, AND CATALYSTS FOR USE THEREOF - Google Patents
PROCEDURE FOR POLYMERIZATION OF OLEFINES, AND CATALYSTS FOR USE THEREOFInfo
- Publication number
- NO148292B NO148292B NO752784A NO752784A NO148292B NO 148292 B NO148292 B NO 148292B NO 752784 A NO752784 A NO 752784A NO 752784 A NO752784 A NO 752784A NO 148292 B NO148292 B NO 148292B
- Authority
- NO
- Norway
- Prior art keywords
- iii
- groups
- saturated
- titanium
- formula
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 64
- 238000006116 polymerization reaction Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 24
- -1 magnesium halide Chemical class 0.000 claims description 82
- 150000003609 titanium compounds Chemical class 0.000 claims description 47
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 40
- 239000010936 titanium Substances 0.000 claims description 39
- 239000007787 solid Substances 0.000 claims description 33
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 29
- 238000010298 pulverizing process Methods 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 229920006395 saturated elastomer Polymers 0.000 claims description 19
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 229920001296 polysiloxane Polymers 0.000 claims description 15
- 239000004711 α-olefin Substances 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001298 alcohols Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- ZQWPRMPSCMSAJU-UHFFFAOYSA-N methyl cyclohexanecarboxylate Chemical compound COC(=O)C1CCCCC1 ZQWPRMPSCMSAJU-UHFFFAOYSA-N 0.000 claims description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- HBJZBPQYTLKQBY-UHFFFAOYSA-N ethyl 2-methylcyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CCCCC1C HBJZBPQYTLKQBY-UHFFFAOYSA-N 0.000 claims description 3
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 claims description 3
- OKLPIZJSDADMHA-UHFFFAOYSA-N methyl 2-methylcyclohexane-1-carboxylate Chemical compound COC(=O)C1CCCCC1C OKLPIZJSDADMHA-UHFFFAOYSA-N 0.000 claims description 3
- IIHIJFJSXPDTNO-UHFFFAOYSA-N methyl cyclopentanecarboxylate Chemical compound COC(=O)C1CCCC1 IIHIJFJSXPDTNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 claims 1
- 229910001623 magnesium bromide Inorganic materials 0.000 claims 1
- 229910001629 magnesium chloride Inorganic materials 0.000 claims 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims 1
- 229910001641 magnesium iodide Inorganic materials 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 15
- 239000012442 inert solvent Substances 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 12
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 125000005907 alkyl ester group Chemical group 0.000 description 10
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000003350 kerosene Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 229920000576 tactic polymer Polymers 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- YQJPWWLJDNCSCN-UHFFFAOYSA-N 1,3-diphenyltetramethyldisiloxane Chemical compound C=1C=CC=CC=1[Si](C)(C)O[Si](C)(C)C1=CC=CC=C1 YQJPWWLJDNCSCN-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 1
- VCYDUTCMKSROID-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VCYDUTCMKSROID-UHFFFAOYSA-N 0.000 description 1
- VLQZJOLYNOGECD-UHFFFAOYSA-N 2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[SiH]1O[SiH](C)O[SiH](C)O1 VLQZJOLYNOGECD-UHFFFAOYSA-N 0.000 description 1
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 1
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- SMRBVBHMRPWMNX-UHFFFAOYSA-M CCO[Ti](Br)(OCC)OCC Chemical compound CCO[Ti](Br)(OCC)OCC SMRBVBHMRPWMNX-UHFFFAOYSA-M 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ICMAFTSLXCXHRK-UHFFFAOYSA-N Ethyl pentanoate Chemical compound CCCCC(=O)OCC ICMAFTSLXCXHRK-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
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-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
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- CJWANOYUFBSCHS-UHFFFAOYSA-L [Br-].[Br-].CCO[Ti+2]OCC Chemical compound [Br-].[Br-].CCO[Ti+2]OCC CJWANOYUFBSCHS-UHFFFAOYSA-L 0.000 description 1
- DJOXOOIJKINTOT-UHFFFAOYSA-K [Br-].[Br-].[Br-].CCO[Ti+3] Chemical compound [Br-].[Br-].[Br-].CCO[Ti+3] DJOXOOIJKINTOT-UHFFFAOYSA-K 0.000 description 1
- YFCGDEUVHLPRCZ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C YFCGDEUVHLPRCZ-UHFFFAOYSA-N 0.000 description 1
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 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
- 208000010668 atopic eczema Diseases 0.000 description 1
- UADWUILHKRXHMM-ZDUSSCGKSA-N benzoflex 181 Natural products CCCC[C@H](CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-ZDUSSCGKSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- FVJWDHCWIYKORU-UHFFFAOYSA-N bis[[[[[dimethyl(trimethylsilyloxy)silyl]oxy-dimethylsilyl]oxy-dimethylsilyl]oxy-dimethylsilyl]oxy]-dimethylsilane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C FVJWDHCWIYKORU-UHFFFAOYSA-N 0.000 description 1
- PYCYBFUMYRVJFK-UHFFFAOYSA-N bis[[dimethyl(phenyl)silyl]oxy]-methyl-phenylsilane Chemical compound C=1C=CC=CC=1[Si](C)(C)O[Si](C)(C=1C=CC=CC=1)O[Si](C)(C)C1=CC=CC=C1 PYCYBFUMYRVJFK-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 description 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- NSYCXGBGJZBZKI-UHFFFAOYSA-L dichlorotitanium;ethanol Chemical compound CCO.CCO.Cl[Ti]Cl NSYCXGBGJZBZKI-UHFFFAOYSA-L 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- QTEITWPJVHAOTN-UHFFFAOYSA-N ethyl 2-chlorobutanoate Chemical compound CCOC(=O)C(Cl)CC QTEITWPJVHAOTN-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HQKSINSCHCDMLS-UHFFFAOYSA-N ethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CC=C21 HQKSINSCHCDMLS-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920001580 isotactic polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- ZKWONARDNQWFKT-UHFFFAOYSA-N methanolate;titanium(2+) Chemical compound CO[Ti]OC ZKWONARDNQWFKT-UHFFFAOYSA-N 0.000 description 1
- JDQLUYWHCUWSJE-UHFFFAOYSA-N methanolate;titanium(3+) Chemical compound [Ti+3].[O-]C.[O-]C.[O-]C JDQLUYWHCUWSJE-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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HMRROBKAACRWBP-UHFFFAOYSA-N methyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=CC2=C1 HMRROBKAACRWBP-UHFFFAOYSA-N 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- 229940102838 methylmethacrylate Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000005209 naphthoic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- AHRFMMRLDGAHBM-UHFFFAOYSA-N propyl 2,2-dichloroacetate Chemical compound CCCOC(=O)C(Cl)Cl AHRFMMRLDGAHBM-UHFFFAOYSA-N 0.000 description 1
- WEHMFTWWOGBHCR-UHFFFAOYSA-N propyl 4-methoxybenzoate Chemical compound CCCOC(=O)C1=CC=C(OC)C=C1 WEHMFTWWOGBHCR-UHFFFAOYSA-N 0.000 description 1
- DVFZYEJUWGWKLC-UHFFFAOYSA-N propyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCCC)=CC=CC2=C1 DVFZYEJUWGWKLC-UHFFFAOYSA-N 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-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
- 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids 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)
Description
Foreliggende oppfinnelse vedrører en fremgangsmåte for frem- The present invention relates to a method for
stilling av meget stereoregulære polyolefiner ved polymeri- position of highly stereoregular polyolefins by polymeri-
sasjon eller kopolymerisasjon av a-olefiner med minst 3 sation or copolymerization of α-olefins with at least 3
karbonatomer i nærvær av en katalysator bestående av carbon atoms in the presence of a catalyst consisting of
(A) en fast titanholdig katalysatorkomponent sammensatt av et organisk kompleks på basis av (A) a solid titanium-containing catalyst component composed of an organic complex based on
(i) et magnesiumhalogenid (i) a magnesium halide
(ii) en Si-holdig forbindelse (ii) a Si-containing compound
(iii) en elektrondonator, og (iii) an electron donor, and
(iv) en titanforbindelse med formelen (iv) a titanium compound of the formula
hvor R er en alkylgruppe, X er et halogenatom, where R is an alkyl group, X is a halogen atom,
og ( er 0 eller et heltall fra 1 til 4, og and ( is 0 or an integer from 1 to 4, and
(B) en organoaluminiumkatalysatorkomponent med for- (B) an organoaluminum catalyst component with pre-
melen the flour
hvori R'-gruppene er like eller forskjellige al- in which the R' groups are the same or different al-
lkylgrupper, og m er et tall fra 1,5 til 3, alkyl groups, and m is a number from 1.5 to 3,
og selve katalysatoren for utøvelse av fremgangsmåten. and the actual catalyst for carrying out the method.
Katalysatorsystemer bestående av faste titanhalogenider og organoaluminiumforbindelser er tidligere blitt anvendt for fremstilling av høyt stereoregulære polymerer av a-olefi- Catalyst systems consisting of solid titanium halides and organoaluminum compounds have previously been used for the production of highly stereoregular polymers of α-olefin
ner. Polymerisasjoner som benytter seg av disse katalysa- down. Polymerizations that make use of these catalysis
torsystemer frembringer meget stereoregulære polymerer, tor systems produce highly stereoregular polymers,
men utbyttet av polymeren pr. enhetsmengde av titankatalysatorkomponenten er enda lavt og et ytterligere trinn trengs for å fjerne katalysatorresten fra den resulterende polymer. Nylig er noen metoder, f.eks. de som er omfattet i japansk utlegningsskrift nr. 16986/73, 16987/73 og 16988/73 foreslått for å fjerne svakhetene i teknikkens stand. Disse metoder prøver å oppnå meget stereoregulære poly (a-olefiner) ved polymerisasjon av a-olefiner slik som but the yield of the polymer per unit amount of the titanium catalyst component is still low and an additional step is needed to remove the catalyst residue from the resulting polymer. Recently, some methods, e.g. those included in Japanese interpretative documents no. 16986/73, 16987/73 and 16988/73 proposed to remove the weaknesses in the state of the art. These methods attempt to obtain highly stereoregular poly(α-olefins) by polymerization of α-olefins such as
propylen ved å anvende en katalysator som inneholder en fast komponent som oppnås ved kopolymerisasjon av en kompleks forbindelse som dannes av et titanhalogenid og en spesifikk elektrondonator sammen med et tørt magnesiumhalogenid, og reaksjonsproduktet fra trialkylaluminium og en propylene by using a catalyst containing a solid component obtained by copolymerization of a complex compound formed by a titanium halide and a specific electron donor together with a dry magnesium halide, and the reaction product of trialkylaluminum and a
spesifikk elektrondonator. Ved disse metodene er imidlertid ennå stereoregulariteten hos den resulterende polymer util-strekkelig og utbyttene av polymeren pr. titanatom er fortsatt utilfredsstillende. I tillegg lider disse metoder en-da av den svakhet at utbyttene av polymeren pr. kloratom i katalysatoren er lave fordi det kopulveriserte produkt har et lavt titaninnhold, at polymerisasjonen må utføres med en lav oppslemningskonsentrasjon på grunn av den åpenbart lave densitet av den resulterende polymeren, slik at metodene faller økonomisk ufordelaktig ut og at katalysatorens polymerisasjonsaktivitet går tapt innen korte tidsrom. specific electron donor. With these methods, however, the stereoregularity of the resulting polymer is still insufficient and the yields of the polymer per titanium atom is still unsatisfactory. In addition, these methods also suffer from the weakness that the yields of the polymer per chlorine atom in the catalyst are low because the copulverized product has a low titanium content, that the polymerization must be carried out with a low slurry concentration due to the obviously low density of the resulting polymer, so that the methods turn out to be economically disadvantageous and that the polymerization activity of the catalyst is lost within a short period of time .
Fransk utlegningsskrift nr. 2.113.313 (mai 29, 1972) omfatter en fremgangsmåte for selektiv fremstilling av enten en ataktisk polymer som et hovedprodukt eller en stereoregulær polymer som et hovedprodukt. Dette patent fastslår at når en Ti-katalysator-komponent som er oppnådd ved å kontakte en titanforbindelse med en blanding av en aktiv type mag-nesiumhalogenidbærer og en vannfri forbindelse av et element fra gruppene I til IV, f.eks. Si, benyttes i ovennevnte prosess fortrinnsvis i en form anbragt på en bærer og deretter modifisert med en elektrondonator, oppnås en stereoregulær polymer som et hovedpunkt. Denne publikasjon il-lustrerer imidlertid bare Si02 som den vannfrie forbindelse av Si. Videre beskrives i denne publikasjon at eterene, tioetere, aminer, fosfiner, ketoner og estere kan brukes som elektrondonatorer, men eksemplifiserer ingen spesifikke forbindelser som faller innen estrene. Isotaktisiteten av polymeren som vises ved alle restene fra ekstraksjon med kokende n-heptan i alle eksemplene fra ovennevnte patent er høyst rundt 70%, og derfor er fremgangsmåten ved dette patent langt fra tilfredsstillende for fremstilling av meget stereoregulære polymerer. På den annen side er elektrondonatoren som anvendes i dette patent for fremstilling av isotaktiske polymerer bare N,N', N","<*->tetrametyl-etylendiamin. Videre brukes bare vannfritt litiumklorid og S1O2 spesifisert i dette patent som vannfri forbindelse av et element i gruppene I til IV. French Patent Application No. 2,113,313 (May 29, 1972) includes a process for the selective preparation of either an atactic polymer as a major product or a stereoregular polymer as a major product. This patent states that when a Ti catalyst component obtained by contacting a titanium compound with a mixture of an active type magnesium halide support and an anhydrous compound of an element from groups I to IV, e.g. Si, used in the above process preferably in a form placed on a support and then modified with an electron donor, a stereoregular polymer is obtained as a main point. However, this publication only illustrates SiO 2 as the anhydrous compound of Si. Furthermore, this publication describes that the ethers, thioethers, amines, phosphines, ketones and esters can be used as electron donors, but does not exemplify any specific compounds that fall within the esters. The isotacticity of the polymer shown by all the residues from extraction with boiling n-heptane in all the examples from the above-mentioned patent is at most around 70%, and therefore the method of this patent is far from satisfactory for the production of highly stereoregular polymers. On the other hand, the electron donor used in this patent for the preparation of isotactic polymers is only N,N',N","<*->tetramethylethylenediamine. Furthermore, only anhydrous lithium chloride and S1O2 specified in this patent are used as the anhydrous compound of an element of groups I to IV.
Man har gjort undersøkelser i den hensikt å unngå svakhetene i de konvensjonelle teknikker og som følge av dette fun-net at en titanholdig katalysatorkomponent sammensatt av et organisk kompleks avledet fra (i) et magnesiumhaloge-nidy (ii) et organo-polysiloksan^ (iii) en organisk karboksylsyreester og (iv) en spesifikk T-forbindelse i kombinasjon med en organoaluminiumforbindelse, frembringer en ut-merket katalysator for fremstilling av meget større regu-lære polyolefiner. Undersøkelsene førte også til den opp-dagelse at ved å bruke denne katalysator kan meget stereoregulære a-olefinpolymerer eller kopolymerer fremstilles i høye utbytter, mens den utmerkede katalytiske aktivitet bibeholdes gjennom et langt tidsrom^og at halogeninnholdet i den resulterende polymer eller kopolymer som må tilskri-ves katalysatoren kan reduseres, og de resulterende polymerer og kopolymerer har en høy åpenbar densitet. Investigations have been carried out with the aim of avoiding the weaknesses of the conventional techniques and as a result of this finding that a titanium-containing catalyst component composed of an organic complex derived from (i) a magnesium halide (ii) an organo-polysiloxane^ (iii ) an organic carboxylic acid ester and (iv) a specific T compound in combination with an organoaluminum compound, produces an excellent catalyst for the production of much larger regular polyolefins. The investigations also led to the discovery that by using this catalyst highly stereoregular α-olefin polymers or copolymers can be produced in high yields, while the excellent catalytic activity is maintained over a long period of time, and that the halogen content of the resulting polymer or copolymer which must be attributed -ves the catalyst can be reduced and the resulting polymers and copolymers have a high apparent density.
Følgelig er et formål ved denne oppfinnelse å tilveiebringe en fremgangsmåte for fremstilling av meget stereoregulære polyolefiner med de ovennevnte forbedrede virkninger, Accordingly, an object of this invention is to provide a process for the production of highly stereoregular polyolefins with the above-mentioned improved effects,
Et annet formål ved oppfinnelsen er å tilveiebringe en katalysator for anvendelse under fremgangsmåten ifølge denne oppfinnelse. Another object of the invention is to provide a catalyst for use in the method according to this invention.
Flere andre mål og fordeler ved denne oppfinnelse vil bli klarere ved den følgende beskrivelse. Several other objects and advantages of this invention will become apparent from the following description.
Polymerisasjonen eller kopolymerisasjonen av a-olefiner The polymerization or copolymerization of α-olefins
med minst 3 karbonatomer, som omtales i denne søknad, inne-befatter homopolymerisasjon av a-olefiner med minst 3 karbonatomer, kopolymerisasjoner av minst 2 av a-olefinene med minst 3 karbonatomer med hverandre, og kopolymerisasjon av a-olefiner med minst 3 karbonatomer med etylen og/eller with at least 3 carbon atoms, which is referred to in this application, includes homopolymerization of α-olefins with at least 3 carbon atoms, copolymerizations of at least 2 of the α-olefins with at least 3 carbon atoms with each other, and copolymerization of α-olefins with at least 3 carbon atoms with ethylene and/or
diolefiner i en mengde på fortrinnsvis opp til 30 mol%. diolefins in an amount of preferably up to 30 mol%.
Eksempler på a-olefiner er propylen, 1-buten, 4-metyl-lpen-ten og 3-metyl-l-buten, og eksempler på diolefiner omfatter konjugerte diolefiner såsom butadien og ikke-konjugerte diener såsom dicyklopentadien, etylidennorbornen og 1,5-heksadien. Examples of α-olefins are propylene, 1-butene, 4-methyl-l-pentene and 3-methyl-1-butene, and examples of diolefins include conjugated diolefins such as butadiene and non-conjugated dienes such as dicyclopentadiene, ethylidene norbornene and 1,5 -hexadiene.
Fremgangsmåten ifølge oppfinnelsen er karakterisert vedThe method according to the invention is characterized by
at det som den Si-holdige forbindelse (ii) anvendes et organisk polysiloksan valgt fra forbindelser med formel Q (Q^SiO) ^^SiO^, hvori Q-gruppene er like eller forskjellige og valgt fra gruppen et hydrogenatom, C^-C^-alkylgrupper, C^-Cg-cykloalkylgrupper og C^-Cg-arylgrupper, med det forbehold at ikke alle Q-grupper er hydrogenatomer samtidig, og n er et heltall fra 1 til 1000; forbindelser med formel (Q2Si0)n, hvori Q er det samme som ovenfor angitt og n' that as the Si-containing compound (ii) an organic polysiloxane selected from compounds of the formula Q (Q^SiO) ^^SiO^, in which the Q groups are the same or different and selected from the group a hydrogen atom, C^-C ^-alkyl groups, C^-Cg cycloalkyl groups and C^-Cg aryl groups, with the proviso that not all Q groups are hydrogen atoms at the same time, and n is an integer from 1 to 1000; compounds of formula (Q2Si0)n, in which Q is the same as above and n'
er et heltall fra 2 til 1000; og forbindelser med formel X(Q^SiQ)^iQ^X, hvori Q og n er som ovenfor angitt, og X is an integer from 2 to 1000; and compounds of formula X(Q^SiQ)^iQ^X, in which Q and n are as above, and X
er et halogenatom, og som elektrondonatoren (iii) anvendes en organisk karboksylsyreester valgt fra estere dannet mellom C2_C8 mette(3e eller umettede alifatiske karboksylsyrer, hvilke eventuelt er substituert med halogenatomer, og alkoholer valgt fra c^~Cg mettede eller umettede alifatiske primære alkoholer, C3_C3 mettede eller umettede alicykliske alkoholer og mettede eller umettede alifatiske primære alkoholer substituert med C^- Cq aromatiske grupper eller halogenatomer; estere dannet mellom C^-C^ aromatiske monokarboksylsyrer og alkoholer valgt fra C^_Cg mettede eller umettede alifatiske primære alkoholer jC^-Cg mettede eller umettede alicykliske alkoholer og mettede eller umettede alifatiske primære alkoholer substituert med Cb ,-Co0 aromatiske grupper eller halogenatomer; og alicykliske karboksylsyreestere valgt fra metylcyklopentankarboksylat, metylheksahydrobenzoat, etylheksahydrobenzoat, metylheksahydrotoluat og etylheksahydrotoluat idet det organiske kompleks er dannet ved å bringe komponenten (i) i kontakt med en is a halogen atom, and as the electron donor (iii) an organic carboxylic acid ester selected from esters formed between C2-C8 saturated or unsaturated aliphatic carboxylic acids, which are optionally substituted with halogen atoms, and alcohols selected from c^~Cg saturated or unsaturated aliphatic primary alcohols is used, C3_C3 saturated or unsaturated alicyclic alcohols and saturated or unsaturated aliphatic primary alcohols substituted with C^-Cq aromatic groups or halogen atoms; esters formed between C^-C^ aromatic monocarboxylic acids and alcohols selected from C^_Cg saturated or unsaturated aliphatic primary alcohols jC^- Cg saturated or unsaturated alicyclic alcohols and saturated or unsaturated aliphatic primary alcohols substituted with Cb ,-Co0 aromatic groups or halogen atoms; and alicyclic carboxylic acid esters selected from methyl cyclopentane carboxylate, methyl hexahydrobenzoate, ethyl hexahydrobenzoate, methyl hexahydrotoluate and ethyl hexahydrotoluate, the organic complex being formed by bringing component (i) into contact with a
kombinasjon av komponentene (ii) og (iii) i et molforhold (i)/(ii)/(iii) på 1/1000-0,01/10-0,005 eller en kombinasjon med komponentene (ii), (iii) og (iv) i et molforhold (i)/(ii)/(iii)/(iv) på 1/1000-0,01/10,0-0,005/100-0,001 under mekaniske pulveriseringsbetingelser og deretter som et ytterligere trinn, behandling av den resulterende pulveriserte blanding med komponenten (iv) uten me-anisk pulverisering. combination of components (ii) and (iii) in a molar ratio (i)/(ii)/(iii) of 1/1000-0.01/10-0.005 or a combination with components (ii), (iii) and ( iv) in a molar ratio (i)/(ii)/(iii)/(iv) of 1/1000-0.01/10.0-0.005/100-0.001 under mechanical pulverization conditions and then as a further step, treatment of the resulting pulverized mixture with component (iv) without mechanical pulverization.
Katalysatoren ifølge oppfinnelsen er tilsvarende sammensatt, slik det fremgår av krav 4. The catalyst according to the invention is similarly composed, as is evident from claim 4.
Det er ønskelig at magnesiumhalogenidet (i) som en be-standdel eller den titanholdige faste katalysatorkomponent It is desirable that the magnesium halide (i) as a component or the titanium-containing solid catalyst component
(A) er så vannfritt som mulig, men innhold av fuktighet er tolererbart i en slik utstrekning at fuktigheten ikke (A) is as anhydrous as possible, but the moisture content is tolerable to such an extent that the moisture does not
vesentlig påvirker katalysatorvirkningen. Halogenidet kan være et som er oppnådd ved dehydratisering av en kommer-siell tilgjengelig vare ved 100 til 400°C under nedsatt trykk før det anvendes. For letthets skyld ved anvendelse anvendes magnesiumhalogenidet fortrinnsvis i form av et pulver som har en gjennomsnittlig partikkeldiameter på 1 til 50 yum. Man når 'det skal pulveriseres ved en mekanisk kontaktbehandling under katalysatorfremstillingen kan også pulveret med større partikkelstørrelse anvendes. Den gjennomsnittlige partikkeldiameter på 1 - 50 pm betyr at minst 80 vekt-% av de totale partikler har en partikkeldiameter på 1 - 50 ^um. significantly affects the catalyst effect. The halide may be one obtained by dehydrating a commercially available product at 100 to 400°C under reduced pressure before it is used. For ease of use, the magnesium halide is preferably used in the form of a powder having an average particle diameter of 1 to 50 µm. When it is to be pulverized by a mechanical contact treatment during the catalyst production, the powder with a larger particle size can also be used. The average particle diameter of 1-50 µm means that at least 80% by weight of the total particles have a particle diameter of 1-50 µm.
Spesifikke eksempler på lineære polysiloksaner med formelen Q(Q2Si0)nSi03 som Si-komponenten (ii) er heksametyl-disiloksan, dekametyltetrasiloksan, tetrakosametylunde-kasiloksan, 3-hydroheptametyltrisiloksan, 3,5-dihydrookta-metyitetrasiloksan ? 3,5,7-trihydrononametylpentasiloksan, tetrametyl-1,3-difenyldisiloksan, pentametyl-1,3,5-tri-fenyltrisiloksan, heptafenyldisiloksan og oktafenyltrisi-loksan. Specific examples of linear polysiloxanes with the formula Q(Q2Si0)nSi03 as the Si component (ii) are hexamethyldisiloxane, decamethyltetrasiloxane, tetracosamethylundecasiloxane, 3-hydroheptamethyltrisiloxane, 3,5-dihydroocta-methyltetrasiloxane ? 3,5,7-trihydrononamethylpentasiloxane, tetramethyl-1,3-diphenyldisiloxane, pentamethyl-1,3,5-tri-phenyltrisiloxane, heptaphenyldisiloxane and octaphenyltrisiloxane.
Spesifikke eksempler på cyklopolysiloksaner med formelen (Q2SiO)n, som Si-komponent (ii) er 2,4,6-trimetylcyklo-trisiloksan, 2,4,6,8-tetrametylcyklotetrasiloksan, 2,4,6,8-tetrametylcyklotetrasiloksan, heksametylcyklo-trisiloksan, oktametylcyklotetrasiloksan, dekametylcyklo-pentasiloksan, dodekametylcykloheksasiloksan, trifenyl-1,3,5-trimetylcyklotrisiloksan, heksafenylcyklotrisilok-san og oktafenylcyklotetrasiloksan. Specific examples of cyclopolysiloxanes with the formula (Q2SiO)n, as Si component (ii) are 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, hexamethylcyclo -trisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, triphenyl-1,3,5-trimethylcyclotrisiloxane, hexaphenylcyclotrisiloxane and octaphenylcyclotetrasiloxane.
Blandt disse organiske polysiloksanene foretrekkes de lineære alkylpolysiloksanene. Metylpolysiloksan og etylpolysiloksan har en viskositet på ikke mer enn 2oo centipoise ved 25°C og foretrekkes spesielt. Among these organic polysiloxanes, the linear alkyl polysiloxanes are preferred. Methylpolysiloxane and ethylpolysiloxane have a viscosity of not more than 2oo centipoise at 25°C and are particularly preferred.
Spesifikke eksempler på de organiske karboksylsyresterne er som komponent (iii) fra den titanholdige faste katalysatorkomponenten (A) er primære alkylestere av enverdige mettede fettsyrer slik. som metylformat, etylacetat, n-amylacetat, 2-etylheksylacetat, n-butylformat, etylbutyrat eller etylvalerat, benzylacetat, allylacetat, primære alkylestere av haloalifatiske karboksylsyrer slik som etylkloracetat, n-propyldikloracetat og etylklorbutyrat, primære alkylestere av umettede fettsyrer slik som metylakrylat, metyl-metakrylat eller i-butylkrotaonat, primære alkylestere av benzosyrer slik som metylbenzoat, etylbenzoat, n-propyl-■benzoat, n- og i-butylbenzoater n- og i-amylbenzoater, n-heksylbenzoat, n-oktylbenzoat og 2-etylheksylbenzoat, primære alkylestere av toluensyre, slik som metyltoluat, etyltoluat, n-propyltoluat, n- og i-butyl- Specific examples of the organic carboxylic acid esters are as component (iii) from the titanium-containing solid catalyst component (A) are primary alkyl esters of monovalent saturated fatty acids such. such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethylhexyl acetate, n-butyl formate, ethyl butyrate or ethyl valerate, benzyl acetate, allyl acetate, primary alkyl esters of haloaliphatic carboxylic acids such as ethyl chloroacetate, n-propyl dichloroacetate and ethyl chlorobutyrate, primary alkyl esters of unsaturated fatty acids such as methyl acrylate, methyl -methacrylate or i-butyl crotaonate, primary alkyl esters of benzoic acids such as methyl benzoate, ethyl benzoate, n-propyl-■benzoate, n- and i-butyl benzoates n- and i-amyl benzoates, n-hexyl benzoate, n-octyl benzoate and 2-ethylhexyl benzoate, primary alkyl esters of toluene acid, such as methyl toluate, ethyl toluate, n-propyl toluate, n- and i-butyl-
toluater, n- og i-amyltoluater eller 2-etylheksyltoluat, primære alkylestere av etylbenzosyre slik som metyletyl-benzoat, etyletylbenzoat, n-propyletylbenzoat og n- og i-butyletylbenzoater, primære alkylestere av xylylenkarbok-sylsyre slik som metyl-3,4-xylylen-l-karboksylat, etyl-3,5-xylylen-l-karboksylat og n-propyl-2,4-xylylen-l-karboksylat, primære alkylestere av anisylsyrer slik som metylanisat, etylanisat, n-propylanisat, og n- og i-butyl-anisater, og primære alkylestere av naftosyrer slik som metylnaftoat, etylnaftoåt, n-propylnaftoat og n- og i-butylnaftoater. toluates, n- and i-amyl toluates or 2-ethylhexyl toluate, primary alkyl esters of ethyl benzoic acid such as methyl ethyl benzoate, ethyl ethyl benzoate, n-propyl ethyl benzoate and n- and i-butyl ethyl benzoates, primary alkyl esters of xylylene carboxylic acid such as methyl 3,4- xylylene-l-carboxylate, ethyl 3,5-xylylene-l-carboxylate and n-propyl-2,4-xylylene-l-carboxylate, primary alkyl esters of anisylic acids such as methylanisate, ethylanisate, n-propylanisate, and n- and i-butyl anisates, and primary alkyl esters of naphthoic acids such as methyl naphthoate, ethyl naphthoate, n-propyl naphthoate and n- and i-butyl naphthoates.
Blant disse primære alkylestrene av aromatiske karboksylsyrer foretrekkes primære C^-C4-alkylestere. Metylbenzoat og etylbenzoater foretrekkes spesielt. Among these primary alkyl esters of aromatic carboxylic acids, primary C 1 -C 4 alkyl esters are preferred. Methyl benzoate and ethyl benzoates are particularly preferred.
Som allerede nevnt kan en del eller det hele av den orga-^ niske karboksylsyreester (iii) anvendes i form av esterbe-handlede produkter eller addukter av forbindelsene (i), (ii) og (iv) ved på forhånd å bringe den i kontakt med disse forbindelser (i), (ii) og (iv).. As already mentioned, part or all of the organic carboxylic acid ester (iii) can be used in the form of ester-treated products or adducts of the compounds (i), (ii) and (iv) by bringing it into contact beforehand with these compounds (i), (ii) and (iv)..
Spesifikke eksempler på titanforbindelsen med formel Ti(OR)^X4_^ (komponent (iv) ) er titantetrahalogenider Specific examples of the titanium compound of formula Ti(OR)^X4_^ (component (iv) ) are titanium tetrahalides
slik som titantetraklorid, titantetrabromid eller titan-tetrajodid, alkoksytitantrihalogenider slik sem metoksytitan-triklorid, etoksytitantriklorid, n-butoksytitantriklorid, etoksytitantribromid eller i-butoksy-titantribromid, dialkoksytitandihalogenider slik som dimetoksytitandiklo-rid, dietoksytitandiklorid, di—n-butoksytitandiklorid eller dietoksytitandibromid, trialkoksytitanmonohalogenider slik som trimetoksytitanklorid, trietoksytitanklorid, tri-n-butoksy-titanklorid og trietoksytitanbromid og tetraal-koksytitan slik som tetrametoksytitan, tetraetoksytitan og tetra-n-butoksytitan. such as titanium tetrachloride, titanium tetrabromide or titanium tetraiodide, alkoxytitanium trihalides such as methoxytitanium trichloride, ethoxytitanium trichloride, n-butoxytitanium trichloride, ethoxytitanium tribromide or i-butoxytitanium tribromide, dimethoxytitanium dihalides such as dimethoxytitanium dichloride, diethoxytitanium dichloride, di-n-butoxytitanium dichloride or diethoxytitanium dibromide, trimethoxytitanium monohalides such such as trimethoxytitanium chloride, triethoxytitanium chloride, tri-n-butoxytitanium chloride and triethoxytitanium bromide and tetraalkoxytitanium such as tetramethoxytitanium, tetraethoxytitanium and tetra-n-butoxytitanium.
Blandt disse foretrekkes titantetrahalogenidene spesielt titantetraklorid. Among these, the titanium tetrahalides, especially titanium tetrachloride, are preferred.
Når et magnesiumhalogenid (i) behandlet med den organiske karboksylsyreesteren (iii) brukes for dannelsen av den faste titanholdige katalysatorkomponenten (A) anvendt i denne oppfinnelse, foretrekkes det å anvende en mekanisk pulveriseringsanordning for å bringe begge i kontakt med hverandre. Som en folge av denne pulveriserende kontakten virker esteren av den organiske syre. innen et vidt område av forhold effektivt på magnesiumhalogenidet. En tilstrekkelig behandlingseffekt kan oppnås selvom forholdet av forstnevnte er lite sammenlignet med sistnevnte When a magnesium halide (i) treated with the organic carboxylic acid ester (iii) is used to form the solid titanium-containing catalyst component (A) used in this invention, it is preferred to use a mechanical pulverizing device to bring both into contact with each other. As a result of this pulverizing contact, the ester of the organic acid acts. over a wide range of conditions effective on the magnesium halide. A sufficient treatment effect can be achieved even if the ratio of the former is small compared to the latter
( i et molarforhold på rund 1/1 til l/2o). (in a molar ratio of around 1/1 to 1/2o).
Når Si-komponenten (ii) behandlet med den organiske karboksylsyreester (iii) anvendes, utfores behandlingen f.eks. ved en metode som består av at den organiske karboksylsyreesteren ved romtemperatur settes til en silisiumforbindelse selv eller opplosning av denne i et egnet inert opplosningsmiddel slik som pentan, heksan, heptan eller kerosen, eller en metode som består av å fremstille en opplosning av den organiske karboksylsyreesteren i det ovennevnte inerte opplosningsmiddel ogsså sette silisiumforbindelsen til opplosningen. Selvfølgelig kan behandlingen utfores innen korte tidsperioder ved forhøyet temperatur, men om onsket kan behandlingen også utfores under kjoling. When the Si component (ii) treated with the organic carboxylic acid ester (iii) is used, the treatment is carried out e.g. by a method consisting of adding the organic carboxylic acid ester at room temperature to a silicon compound itself or dissolving this in a suitable inert solvent such as pentane, hexane, heptane or kerosene, or a method consisting of preparing a solution of the organic carboxylic acid ester in the above inert solvent also add the silicon compound to the solution. Of course, the treatment can be carried out within short periods of time at an elevated temperature, but if desired, the treatment can also be carried out while dressing.
Når titanforbindelsen (iv) blir anvendt i form av et addukt When the titanium compound (iv) is used in the form of an adduct
av seg selv med den organiske karboksylsyreester (iii),kan adduktet fremstilles ved tilsetning av den organiske karboksylsyreester (iii) i en ekvimolar eller storre mengde ( beregnet på basis av esteren) til selve titanforbindelsen )( hvis den er flytende ) eller en opplosning av den i ovennevnte inerte opplosningsmiddel ( hvis den er fast ) og atskille den resulterende utfelling ved filtrasjon. Selv når titanforbindelsen er flytende, kan den anvendes i den adduktdannende reaksjonen i form av opplosning i ovennevnte inerte opplosningsmiddel. Vaskingen av den resulterende fellingen (fjerning av ikke-reagert titanforbindelse og organisk karboksylsyreester) kan også utfores ved å anvende ovennevnte opplosningsmiddel. by itself with the organic carboxylic acid ester (iii), the adduct can be prepared by adding the organic carboxylic acid ester (iii) in an equimolar or greater amount (calculated on the basis of the ester) to the titanium compound itself (if it is liquid) or a solution of it in the above inert solvent (if solid) and separate the resulting precipitate by filtration. Even when the titanium compound is liquid, it can be used in the adduct-forming reaction in the form of dissolution in the above-mentioned inert solvent. The washing of the resulting precipitate (removal of unreacted titanium compound and organic carboxylic acid ester) can also be carried out by using the above-mentioned solvent.
Forholdet av vannfritt magnesiumhalogenid (i)/Si-komponent (ii)/organisk karboksylsyreester (iii)/titanforbindelsen (iv) som utgangsmaterialer for katalysatorkomponenten (A) er ikke spesielt begrenset men er vanligvis l/looo-o,ol/lo-o,po5/ loo-o,ool, fortrinnsvis l/lo-o,ol/l-o,ol/3o-o,ol. The ratio of anhydrous magnesium halide (i)/Si component (ii)/organic carboxylic acid ester (iii)/titanium compound (iv) as starting materials for the catalyst component (A) is not particularly limited but is usually l/looo-o,ol/lo-o ,po5/ loo-o,ool, preferably l/lo-o,ol/l-o,ol/3o-o,ol.
Fortrinnsvis fremstilles den titanholdige faste katalysatorkomponenten (A) ved å bringe komponentene (i), (ii), (iii) og (iv) i kontakt med hverandre under pulveriserende betingelser. Preferably, the titanium-containing solid catalyst component (A) is prepared by bringing components (i), (ii), (iii) and (iv) into contact with each other under pulverizing conditions.
Et antall forskjellige måter er mulige med hensyn til tilsetn ings-orden for disse komponentene, og tilsetningsmetoden og kontakfe-metoden og noen eksempler er vist nedenfor. A number of different ways are possible with regard to the order of addition of these components, and the addition method and contact method and some examples are shown below.
(1) Det vannfrie megnesiumhalogenidet (i), det organiske polysiloksanet (ii), den organiske karboksylsyreesteren (iii) (1) The anhydrous magnesium halide (i), the organic polysiloxane (ii), the organic carboxylic acid ester (iii)
og titanforbindelsen (iv) bringes i grundig kontakt med hverandre ved en mekanisk pulveriseringsanordning ( som skal refereres til som pulveriserende kontakt), og den resulterende titanholdige faste komponenten behandles fortrinnsvis med komponenten (iv) eller oppløsningen av denne i et inert opplosningsmiddel. and the titanium compound (iv) are brought into thorough contact with each other by a mechanical pulverizing device (to be referred to as pulverizing contact), and the resulting titanium-containing solid component is preferably treated with the component (iv) or its solution in an inert solvent.
(2) Magnesiumhalogenidet (i), det organiske polysiloksanet (ii) og den organiske karboksylsyreesteren kontaktes pulveriserende. Den resulterende faste komponenten behandles ved suspensjon i titanforbindelsen (iv) eller opplosning av den i et inert opplosningsmiddel. Eller den faste komponenten og titanforbindelsen (iv) kontaktes pulveriserende i praktisk torr tilstand og behandles så ved suspensjon fortrinnsvis i titanforbindelsen (2) The magnesium halide (i), the organic polysiloxane (ii) and the organic carboxylic acid ester are pulverized. The resulting solid component is treated by suspending it in the titanium compound (iv) or dissolving it in an inert solvent. Or the solid component and the titanium compound (iv) are pulverized in a practically dry state and then treated by suspension, preferably in the titanium compound
(iv) eller opplosning av denne i et inert opplosningsmiddel. (iv) or dissolving it in an inert solvent.
(3) Det vannfrie magnesiumhalogenidet (i) og den organiske karboksylsyreesteren (iii) kontaktes pulveriserende og kontaktes videre pulveriserende med det organiske polysiloksanet (ii) for å danne en fast komponent. Eller magnesiumhalogenidet (i) og Si-komponenten (ii) kontaktes forst pulveriserende og så med (3) The anhydrous magnesium halide (i) and the organic carboxylic acid ester (iii) are pulverized and further pulverized with the organic polysiloxane (ii) to form a solid component. Or the magnesium halide (i) and the Si component (ii) are contacted first by pulverizing and then with
den organiske karboksylsyreesteren (ii) for å danne en fast komponent. Enhver slik fast komponent behandles under suspensjon i titanforbindelsen (iv) eller opplosning av den i et inert opplosningsmiddel. Eller den faste komponenten kontaktes pulveriserende med titankomponenten (iv) i praktis torr tilstand og the organic carboxylic acid ester (ii) to form a solid component. Any such solid component is treated in suspension in the titanium compound (iv) or dissolving it in an inert solvent. Or the solid component is pulverized in contact with the titanium component (iv) in a practically dry state and
og behandles så fortrinnsvis ved suspensjon i titanforbindelsen (iv) eller opplosning av denne i et inert opplosningsmiddel. and is then preferably treated by suspension in the titanium compound (iv) or dissolving this in an inert solvent.
(4) Det vannfrie magnesiumhalogenidet (i), det organiske polysiloksanet (ii) og et addukt av titanforbindelsen (iv) (4) The anhydrous magnesium halide (i), the organic polysiloxane (ii) and an adduct of the titanium compound (iv)
og den organiske karboksylsyreesteren (iii) blir kontaktet i pulverform, og den resulterende faste titanholdige komponenten behandles fortrinnsvis ved suspensjon i titanforbindelsen (iv) eller opplosning av denne i inert opplosningsmiddel. and the organic carboxylic acid ester (iii) is contacted in powder form, and the resulting solid titanium-containing component is preferably treated by suspension in the titanium compound (iv) or dissolution thereof in an inert solvent.
(5) Det vannfrie magnesiumhalogenidet (i) og det organiske polysiloksanet (ii) kontaktes pulverisernde og kontaktes så (5) The anhydrous magnesium halide (i) and the organic polysiloxane (ii) are pulverized and then contacted
videre pulveriserende med et addukt av titanforbindelsen (iv) further pulverizing with an adduct of the titanium compound (iv)
og den organiske karboksylsyreesteren (iii). Den resulterende titanholdige faste komponenten behandles fortrinnsvis ved suspensjon i titanforbindelsen (iv) eller opplosning av denne i et inert opplosningsmiddel. and the organic carboxylic acid ester (iii). The resulting titanium-containing solid component is preferably treated by suspending it in the titanium compound (iv) or dissolving it in an inert solvent.
(6) I fremgangsmåtene for (1) og (3) ovenfor anvendes titanforbindelsen (iv) i form av et addukt med den organiske karboksylsyreesteren (iii). (7) Det vannfrie magnesiumhalogenidet (i), det organiske polysiloksanet (ii), titanforbindelsen (iv) og et addukt av titanforbindelsen (iv) og den organiske karboksylsyreesteren (iii) kontaktes pulveriserende og den resulterende titanholdige faste komponenten behandles fortrinnsvis ved suspensjon i titanforbindelsen (iv) eller en opplosning av denne i et inert opplosningsmiddel. (8) I fremgangsmåten i avsnitt (7) ovenfor, tilsettes den organiske karboksylsyreesteren (iii) også til det pulveriserende kontaktsystem. (6) In the methods for (1) and (3) above, the titanium compound (iv) is used in the form of an adduct with the organic carboxylic acid ester (iii). (7) The anhydrous magnesium halide (i), the organic polysiloxane (ii), the titanium compound (iv) and an adduct of the titanium compound (iv) and the organic carboxylic acid ester (iii) are pulverized and the resulting titanium-containing solid component is preferably treated by suspension in the titanium compound (iv) or a solution thereof in an inert solvent. (8) In the method in section (7) above, the organic carboxylic acid ester (iii) is also added to the pulverizing contact system.
Den pulveriserende kontaktanordningen ved fremstilling av den titanholdige faste titankomponenten (A) i foreliggende oppfinnelse kan f.eks. bestå av anordninger som bruker en roterende kulemolle, en vibrerende kulemolle eller en slagmblle Som et resultat av kontakt med en slik pulveriserende kontaktanordning virker den organiske karboksylsyreesteren (iii), det organiske polysiloksanet (ii) og titanforbindelsen (iv) oyeblikkelig på den aktive overflate som oppstår ved pulveriseringen av magnesiumhalogenidet (i) under dannelsen av et organisk kompleks, hvis kjemiske struktur ennå ikke er oppklart. Dette kan fastslås ved det faktum at rontgendifraksjonsspekteret av magnesiumhalogenidpulveret forandres. The pulverizing contact device in the production of the titanium-containing solid titanium component (A) in the present invention can e.g. consist of devices using a rotating ball spring, a vibrating ball spring or an impact bubble As a result of contact with such a pulverizing contact device, the organic carboxylic acid ester (iii), the organic polysiloxane (ii) and the titanium compound (iv) act instantaneously on the active surface which arises from the pulverization of the magnesium halide (i) during the formation of an organic complex, the chemical structure of which has not yet been elucidated. This can be determined by the fact that the X-ray diffraction spectrum of the magnesium halide powder changes.
Behandlingsbetingelsene som anvendes for pulveriserende kontakt The processing conditions used for pulverizing contact
av to eller flere av utgangsmaterialene for katalysatorkomponenten (A) ved anvendelse av forskjellige moller kan utvelges som folger: of two or more of the starting materials for the catalyst component (A) using different moles can be selected as follows:
Ved å ta bruken av en roterende kulemolle som et eksempel, Taking the use of a rotating ball bearing as an example,
ble loo kuler,med en diameter på 15 mm fremstilt av rustfritt stål ( SUS 32) innelukket i en sylindrisk kulebeholder fremstilt av rustfritt stål ( SUS 32) og har et indre innhold på were loo balls, with a diameter of 15 mm made of stainless steel (SUS 32) enclosed in a cylindrical ball container made of stainless steel (SUS 32) and has an internal content of
8oo ml og en invendig diameter på loo mm. Når 2o - 4o g av materialene plasseres deri, utfores pulveriseringsbehandlingen vanligvis i minst 48 timer, fortrinnsvis minst 72 timer ved en hastighet på 125 omdr./min. Temperaturen under pulv erisas jons-behandlingen ligger vanligvis nær romtemperaturen. Hvis det er en markert varmeavgivelse, kjoles systemet fortrinnsvis.og den pulveriserende kontakten utfores ved en temperatur som er lavere enn romtemperatur. 8oo ml and an internal diameter of loo mm. When 20 - 40 g of the materials are placed therein, the pulverization treatment is usually carried out for at least 48 hours, preferably at least 72 hours at a speed of 125 rpm. The temperature during the powder ion treatment is usually close to room temperature. If there is a marked heat release, the system is preferably cooled and the pulverizing contact is carried out at a temperature lower than room temperature.
Behandlingen av den faste komponenten som oppnås ved pulveriserende kontakt av utgangsmaterialene av den faste komponenten (A) The processing of the solid component obtained by pulverizing contact of the starting materials of the solid component (A)
med titanforbindelsen (iv) kan hensiktsmessig utfores ved å with the titanium compound (iv) can conveniently be carried out by
rore blandingen vanligvis ved 4o°C til kokepunktet for den behandlede blandingen i minst en time. Alternativt kan dette oppnås ved pulveriserende kontakt under ovenfor anforte pulveriseringsbetingelser i minst loo timer ved å anvende kulemollen. stirring the mixture usually at 4o°C to the boiling point of the treated mixture for at least one hour. Alternatively, this can be achieved by pulverizing contact under the above stated pulverizing conditions for at least 10 hours by using the ball mold.
Når titanforbindelser anvendes ved to forskjellige anledninger When titanium compounds are used on two different occasions
i ovennenvte behandlingsprosedyre, kan de være like eller forskjellige fra hverandre så lenge de velges blandt forbindelser med ovenfor angitte generelle formler. in the above treatment procedure, they may be the same or different from each other as long as they are selected from among compounds of the above general formulas.
Den faste titanholdige katalysatorkomponenten (A) oppstår etter atskillelse av det organiske faste komplekset fremstilt på ovenfor angitte måte fra suspensjonen.Fortrinnsvis vaskes det fullstendig med heksan eller et annet inert flytende medium slik at den frie titanforbindelsen (iv) ikke lenger kan påvises i vaske-væsken. The solid titanium-containing catalyst component (A) occurs after separation of the organic solid complex produced in the above-mentioned manner from the suspension. It is preferably washed completely with hexane or another inert liquid medium so that the free titanium compound (iv) can no longer be detected in the washing the liquid.
Katalysatorkomponenten (B) som skal kombineres med katalysatorkomponenten (A) i foreliggende oppfinnelsen er en organoaluminiumforbindelse med den generelle formel R' m Al(0R')Jo -m hvori R' er en alkylgruppe, fortrinnsvis en C^-C^ rettlinjet eller forgrenet alkylgruppe, de to eller flere R' gruppene er identiske eller forskjellige og m er et tall i området 1,5 = m - 3. The catalyst component (B) to be combined with the catalyst component (A) in the present invention is an organoaluminum compound with the general formula R' m Al(0R')Jo -m in which R' is an alkyl group, preferably a C^-C^ linear or branched alkyl group, the two or more R' groups are identical or different and m is a number in the range 1.5 = m - 3.
Eksempler på organoaluminiumforbindelsen er som folger: Examples of the organoaluminum compound are as follows:
(1) Når m er 3, er forbindelsen en trialkylaluminium. Spesifikke eksempler er trimetylaluminium, trietylaluminium, tri-n- og -i-propylaluminiumer, tri-n- og -i-butylaluminium og triheksylaluminium. Trietylaluminium og tributylaluminium er foretrukket. De kan også anvendes i kombinasjon på to eller flere. Hvis onsket kan trialkylaluminiumet omsettes med den organiske karboksylsyreesteren for anvendelse. Denne reaksjonen kan utfores i polymerisasjonssystemet for initieringen av polymerisasjonen, eller den kan utfores separat og reaksjonsproduktet settes så til polymerisasjonssystemet. Reaksjonen forloper tilstrekkelig ved å kontakte frie alkylaluminiumet direkte med en organisk karboksylsyreester ( eller ved å anvende en av dem som en opplosning i et inert opplosningsmiddel). Mengdeforholdet mellom disse materialene er slik at andelen av trialkylaluminiumet vanligvis er 2 til loo mol ( basert på aluminiumatomet ) pr. gramekvivalent av estergruppen av den organiske karboksylsyreesteren. Den organiske karboksylsyreesteren kan. velges fra de forskjellige organiske karboksylsyreesterene som komponent (iii) i dannelsen av katalysatorkomponenten (A). Normalt kan den være av samme type syreester som den anvendt ved dannelsen av katalysatorkomponenten (A). (2) Når m er minst 1,5 men under 3 (1,5 m<3), er ovenstående aluminiumforbindelse et delvis alkoksylert alkylaluminium. (1) When m is 3, the compound is a trialkylaluminum. Specific examples are trimethylaluminum, triethylaluminum, tri-n- and -i-propylaluminums, tri-n- and -i-butylaluminum and trihexylaluminum. Triethylaluminum and tributylaluminum are preferred. They can also be used in combination of two or more. If desired, the trialkyl aluminum can be reacted with the organic carboxylic acid ester for use. This reaction can be carried out in the polymerization system for the initiation of the polymerization, or it can be carried out separately and the reaction product then added to the polymerization system. The reaction proceeds sufficiently by contacting the free alkyl aluminum directly with an organic carboxylic acid ester (or by using one of them as a solution in an inert solvent). The quantity ratio between these materials is such that the proportion of the trialkyl aluminum is usually 2 to 10 mol (based on the aluminum atom) per gram equivalent of the ester group of the organic carboxylic acid ester. The organic carboxylic acid ester can. is selected from the various organic carboxylic acid esters as component (iii) in the formation of the catalyst component (A). Normally, it can be of the same type of acid ester as that used in the formation of the catalyst component (A). (2) When m is at least 1.5 but less than 3 (1.5 m<3), the above aluminum compound is a partially alkylated alkylaluminum.
En slik alkylaluminium fremstilles f.eks. ved tilsetning av Such an alkyl aluminum is produced, e.g. by addition of
en beregnet mengde av en alkohol til et trialkylaluminium eller dialkylaluminiumhydrid. Da denne reaksjonen er voldsom, anvendes minst en av dem fortrinnsvis som en opplosning i et inert opplosningsmiddel for å få reaksjonen til å forldpe mildt. a calculated amount of an alcohol to a trialkylaluminum or dialkylaluminum hydride. Since this reaction is violent, at least one of them is preferably used as a solution in an inert solvent to make the reaction proceed gently.
For å polymerisere eller kopolymerisere a-olefiner med minst 3-karbonatomer under anvendelse av katalysatoren bestående av den faste titanholdige katalysatorkomponenten (A) og organo-aluminiumkatalysatorkomponenten (B) kan hensiktsmessig gi polymerisasjonsbetingelsene som er kjent anvendt i polymerisasjoner eller kopolymerisasjoner av a-olefiner ved anvendelse av Ziegler-typen katalysatorer velges. Vanligvis kan anvendes polymerisasjonstemperaturer på fra romtemperatur til rundt 2oo°C og trykk fraatmosfæretrykk til rundt 5o kg/cm^. Polymerisasjonen eller kopolymerisasjonene kan utfores i nærvær eller i fravær av et inert flytende medium. Eksempler på det flytende medium er pentan, heksan, heptan, iso-oktan og kerosen. Hvor polymerisasjonen eller kopolymerisasjonen utfores i fravær av et flytende medium, kan den gjennomføres i nærvær av en flytende olefinmonomer eller den utfores i dampfasen, f.eks. ved å anvende en fluidisert bedkatalysator. To polymerize or copolymerize α-olefins with at least 3 carbon atoms using the catalyst consisting of the solid titanium-containing catalyst component (A) and the organo-aluminum catalyst component (B) can conveniently provide the polymerization conditions known to be used in polymerizations or copolymerizations of α-olefins by the use of Ziegler-type catalysts is chosen. Generally, polymerization temperatures of from room temperature to around 2oo°C and pressures from atmospheric pressure to around 5o kg/cm 2 can be used. The polymerization or copolymerizations can be carried out in the presence or in the absence of an inert liquid medium. Examples of the liquid medium are pentane, hexane, heptane, iso-octane and kerosene. Where the polymerization or copolymerization is carried out in the absence of a liquid medium, it may be carried out in the presence of a liquid olefin monomer or it may be carried out in the vapor phase, e.g. by using a fluidized bed catalyst.
Katalysatorkonsentrasjonen som skal anvendes i polymerisasjonssystemet ved polymerisasjonen kan endres om onsket. F. eks. The catalyst concentration to be used in the polymerization system during the polymerization can be changed if desired. For example
i fastfasepolymerisasjoner anvendes den titanholdige faste katalysatorkomponenten (A) i en konsentrasjon på vangigvis o,oool til l,o m-mol/liter beregnet som titanatom og katalysatorkomponenten (B) anvendes i en konsentrasjon på vanligvis 1/1 til loo/l, fortrinnsvis 1/1 til 3o/l med hensyn til aluminiumatom/ titanatom-forholdet. Ved dampfasepolymerisasjoner kan den titanholdige faste katalysatorkomponenten (A) anvendes i en konsentrasjon på o/ool - o,5 m-mol ( beregnet som titanatom) og katalysatorkomponenten (B) i en mengde på o,ol - 5 m-mol (beregnet som aluminiumatom), begge pr. liter av volumet for reaksjonssonen. in solid-phase polymerizations, the titanium-containing solid catalyst component (A) is used in a concentration of usually 0.oool to 1.0 m-mol/liter calculated as titanium atoms and the catalyst component (B) is used in a concentration of usually 1/1 to 100/l, preferably 1/1 to 3o/l with respect to the aluminum atom/titanium atom ratio. In vapor phase polymerizations, the titanium-containing solid catalyst component (A) can be used in a concentration of o/ool - o.5 m-mol (calculated as titanium atoms) and the catalyst component (B) in an amount of o.ol - 5 m-mol (calculated as aluminum atom), both per liters of the volume for the reaction zone.
For å senke molekylarvekten i den resulterende polymeren ( i den hensikt å oke smelteindeksen for polymeren), kan hydrogen forårsakes å være tilstede i polymerisasjonssystemet.r In order to lower the molecular weight of the resulting polymer (in order to increase the melt index of the polymer), hydrogen can be caused to be present in the polymerization system.
De folgende eksempla: og sammenligningseksempler illustrer foreliggende oppfinnelse mer spesielt. The following examples and comparative examples illustrate the present invention more particularly.
EKSEM PEL 1 Eczema PEL 1
Fremstilling av katalysatorkomponenten (A): Preparation of the catalyst component (A):
En 800 ml rustfritt stål kulemolle ( SUS 32) med en invendig diameter på loo mm inneholdende loo rustfritt stålkuler (SUS 32) med en diameter på 15 mm ble fyllt med 2o g vannfritt magnesiumklorid, 6,0 ml etylbenzoat og 3,o ml metylpolysiloksan ( med en viskositet på 2o centipoise ved 25°C) i en nitrogenatmosfære og kontaktet pulveriserende loo timer ved en omdreiningshastighet på 125 omdr./min. Det resulterende faste produktet ble suspendert 1 15o ml titantetraklorid og suspensjonen ble rort ved 8o°C i 2 timer, så ble den faste komponenten samlet ved filtrasjon og vasket med renset heksan inntil fritt titantetraklorid ikke lenger kunne påvises. Den resulterende komponenten inneholdt 4,1 vekt-% titan og 58,2 vekt-% klor som atomer. An 800 ml stainless steel ball mold (SUS 32) with an internal diameter of 10 mm containing 15 mm diameter stainless steel balls (SUS 32) was filled with 20 g of anhydrous magnesium chloride, 6.0 ml of ethyl benzoate and 3.0 ml of methylpolysiloxane (with a viscosity of 20 centipoise at 25°C) in a nitrogen atmosphere and contacted pulverizing 10 hours at a rotational speed of 125 rpm. The resulting solid was suspended in 1150 ml of titanium tetrachloride and the suspension was stirred at 80°C for 2 hours, then the solid component was collected by filtration and washed with purified hexane until free titanium tetrachloride could no longer be detected. The resulting component contained 4.1 wt% titanium and 58.2 wt% chlorine atoms.
Polymerisasjon: Polymerization:
En 2 liters autoklav ble fylt med o,o5 ml ( o,375 m-mol), A 2 liter autoclave was filled with o.o5 ml (o.375 m-mol),
43,8 mg ( o,o375 m-mol beregnet som titanatom) av den titanholdige faste komponenten (A) erholdt ovenfor og 7 5o ml kerosen ( renset kerosen) tilstrekkelig fri for oksygen og fuktighet. Polymerisasjonssystemet ble varmet og når temperaturen nådde 7o°C,ble propylen innfort. Polymerisasjonen av propylen ble startet ved et totaltrykk på 7,o kg/cm . Etter å ha fortsatt polymerisasjonen ved 7o°C 43.8 mg (o.o375 m-mol calculated as titanium atom) of the titanium-containing solid component (A) obtained above and 7 5o ml of kerosene (purified kerosene) sufficiently free of oxygen and moisture. The polymerization system was heated and when the temperature reached 70°C, propylene was introduced. The polymerization of propylene was started at a total pressure of 7.0 kg/cm . After continuing the polymerization at 7o°C
i 3 timer ble innforingen av propylen stanset. Innsiden av autoklaven ble kjolt til romtemperatur og katalysatoren spaltet ved tilsetning av metanol. Den faste komponenten ble samlet ved filtrasjon, vasket med metanol og torket til å gi 41o,3 g polypropylen som et hvitt pulver. Residuet fra kokende n-heptanekstraksjon (II) av pulveret var 94,5% og dets åpenbare densitet var o,3o g/ml. for 3 hours the introduction of propylene was stopped. The inside of the autoclave was cooled to room temperature and the catalyst cleaved by the addition of methanol. The solid component was collected by filtration, washed with methanol and dried to give 410.3 g of polypropylene as a white powder. The residue from boiling n-heptane extraction (II) of the powder was 94.5% and its apparent density was 0.30 g/ml.
På den annen side kan oppkonsentrering av væskefasen 15,1 g av On the other hand, concentration of the liquid phase can 15.1 g of
en opplosningsmiddel-lbslig polymer. a solvent-labile polymer.
Den gjennomsnittlige spesifikke polymerisasjonsaktivitetenper titanatom i katalysatoren som ble anvendt ovenfor var 54o g/Ti-m M. hr.atm. The average specific polymerization activity per titanium atom in the catalyst used above was 540 g/Ti-m M.hr.atm.
S AMMENLIGNINGSEKSEMPEL 1 COMPARISON EXAMPLE 1
Fremstilling av en titanholdig katalysatorkomponent: Preparation of a titanium-containing catalyst component:
En kulemolle av samme type som anvendt i eksempel 1 fylt med A ball mold of the same type as used in example 1 filled with
2o g vanfritt magnesiumklorid.og 17,8 g av et addukt med gjennomsnittlig sammensetning av formelen TiCl^.CgH^COOC^H^, 2o g of anhydrous magnesium chloride.and 17.8 g of an adduct with an average composition of the formula TiCl^.CgH^COOC^H^,
og de ble pulveriserende kontaktet under samme betingelser som i eksempel 1 i loo timer ved en hastighet på 125 omdr./min. and they were pulverizingly contacted under the same conditions as in Example 1 for 10 hours at a speed of 125 rpm.
Den resulterende faste titankatalysatorkomponenten ( svarende The resulting solid titanium catalyst component (corresponding
til komponenten (A) i eksempel 1) ble betraktelig agglomerert i en kulemolle og var vanskelig å oppnå i pulverform. En del av faste komponenten ble vasket med 1 1 renset heksan til samme grad som i eksempel 1 og torket for å danne en titankatalysatorkomponent. Titankatalysatorkomponenten inneholdt 4,2 vekt-% og 6,3 vekt-% regnet som atomer. to component (A) in example 1) was considerably agglomerated in a ball mill and was difficult to obtain in powder form. A portion of the solid component was washed with 1 L of purified hexane to the same extent as in Example 1 and dried to form a titanium catalyst component. The titanium catalyst component contained 4.2% by weight and 6.3% by weight calculated as atoms.
Polymerisasjon: Polymerization:
Propylen ble polymerisert under de samme betingelser som i eksempel 1 ved å anvende 114 mg av ovenfor oppnådde titankatalysatorkomponent. Det ble bare oppnådd 8,8 g polypropylen som et hvitt pulver og 1,7 g en opplosningsmiddel-loslig polymer. The propylene was polymerized under the same conditions as in example 1 by using 114 mg of the titanium catalyst component obtained above. Only 8.8 g of polypropylene as a white powder and 1.7 g of a solvent-soluble polymer were obtained.
EKSEMPLENE 2, 3, 4 og 5- EXAMPLES 2, 3, 4 and 5-
I hver sats ble en titankatalysatorkomponent (A) fremstilt In each batch, a titanium catalyst component (A) was prepared
på samme måte som i eksempel 1 bortsett fra at polysiloksanene som er beskrevet i tabell 1 ble anvendt. Propylen ble polymerisert under de samme betingelser som i eksempel 1 ved å anvende den resulterende titankatalysatorkomponenten i mengden som indikert i tabell 1. Resultatene er også vist i tabell 1. in the same way as in Example 1 except that the polysiloxanes described in Table 1 were used. Propylene was polymerized under the same conditions as in Example 1 using the resulting titanium catalyst component in the amount indicated in Table 1. The results are also shown in Table 1.
EKSEMPLENE 6- 8 EXAMPLES 6-8
I hver sats ble katalysatorkomponent (A) fremstilt under samme betingelser som i eksempel 1 bortsett fra at hver av de substituer-te benzosyreesterne vist i tabell 2 ble anvendt i mengden vist i tabell 2. Propylen ble polymerisert på samme måte som i eksempel 1 ved å anvende katalysatorkomponent (A) i en mengde som vist i tabell 2. Resultatene er vist i tabell 2. In each batch, catalyst component (A) was prepared under the same conditions as in example 1, except that each of the substituted benzoic acid esters shown in table 2 was used in the amount shown in table 2. The propylene was polymerized in the same way as in example 1 by to use catalyst component (A) in an amount as shown in table 2. The results are shown in table 2.
EKSEMPEL 9 EXAMPLE 9
Fremstilling av katalysatorkomponent (A) : Preparation of catalyst component (A):
En fast komponent ble fremstilt ved kulemollebehandling av vannfritt magnesiumklorid, etylbenzoat og metylhydropolysiloksan åpå samme måte som i eksempel 1. Den resulterende faste komponenten ble suspendert i loo ml kerosen inneholdende 5o ml titantetraklorid og således behandlet ved loo°C i 2 timer under roring. Den faste . komponenten ble oppsamlet ved filtrering og vasket med renset heksan inntil fritt titantetraklorid ikke lenger kunne påvises. A solid component was prepared by ball mill treatment of anhydrous magnesium chloride, ethyl benzoate and methylhydropolysiloxane in the same manner as in Example 1. The resulting solid component was suspended in 10 ml of kerosene containing 50 ml of titanium tetrachloride and thus treated at 10°C for 2 hours with stirring. The fixed . the component was collected by filtration and washed with purified hexane until free titanium tetrachloride could no longer be detected.
Den resulterende katalysatorkomponenten (A) inneholdt 3,o vekt-% titan og 61,2 vekt-% klor beregnet som atomer. The resulting catalyst component (A) contained 3.0 wt% titanium and 61.2 wt% chlorine calculated as atoms.
Polymerisasjon: Polymerization:
En 21iters autoklav ble fylt med 75o ml renset kerosen, o,o95 A 21 liter autoclave was filled with 75o ml of purified kerosene, o.o95
ml ( o,375 m-mol) triisobutylaluminium og 59,5 ml ( o,o375 m-mol beregnet som titanatom) katalysatorkomponent (A). Polymerisasjonssystemet ble oppvarmet og når temperaturen nådde 7o°C, ble propylen innfort. Polymerisasjonen av propylenet ble startet ved et totaltrykk på 7,o kg/cm 2. Polymerisasjonen ble utfort 5 timer ved 7o°C under roring og så ble innfbringen av propylen stoppet. Innsiden av autoklaven ble kjolt til romtemperatur og den faste komponenten ble oppsamlet ved filtrering, vasket med metanol og tbrket til å gi 39o,4 g polypropylen som et hvitt pulver og 12,1 g av en opplosningsmiddel-loslig polymer. ml (o.375 m-mol) triisobutylaluminum and 59.5 ml (o.o375 m-mol calculated as titanium atom) catalyst component (A). The polymerization system was heated and when the temperature reached 70°C, propylene was introduced. The polymerization of the propylene was started at a total pressure of 7.0 kg/cm 2 . The polymerization was carried out for 5 hours at 7o°C with stirring and then the introduction of the propylene was stopped. The interior of the autoclave was cooled to room temperature and the solid component was collected by filtration, washed with methanol and used to give 390.4 g of polypropylene as a white powder and 12.1 g of a solvent-soluble polymer.
Den pulverformige polymeren hadde en n-heptanekstråksjonsrest The powdered polymer had an n-heptane extraction residue
på 96,4 % og en åpenbartetthet på o,31 g/ml. Den gjennomsnittlige spesifikke polymerisasjonsaktiviteten til katalysatoren var 3o6 g polypropylen/Ti-mmol.hr.atm. of 96.4% and an apparent density of o.31 g/ml. The average specific polymerization activity of the catalyst was 306 g polypropylene/Ti-mmol.hr.atm.
EKSEMPLENE lo til 14 THE EXAMPLES laughed until 14
I hver sats ble en katalysatorkomponent (A) fremstilt under In each batch, a catalyst component (A) was prepared below
de samme betingelser som i eksempel 1 bortsett fra at hver av polysiloksanene vist i tabell 3 ble anvendt i stedet for metylpolysiloksanet. Propylen ble polymerisert på samme måte som i eksempel 1 ved å anvende katalysatorkomponenten (A) i mengden vist i tabell 3. Resultatene er vist i tabell 3. the same conditions as in Example 1 except that each of the polysiloxanes shown in Table 3 was used instead of the methylpolysiloxane. The propylene was polymerized in the same way as in example 1 by using the catalyst component (A) in the amount shown in table 3. The results are shown in table 3.
Claims (4)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP49091181A JPS5120297A (en) | 1974-08-10 | 1974-08-10 | Arufua orefuinno koritsutaikisokuseijugohoho |
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NO752784L NO752784L (en) | 1976-02-11 |
NO148292B true NO148292B (en) | 1983-06-06 |
NO148292C NO148292C (en) | 1983-09-14 |
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JP (1) | JPS5120297A (en) |
AT (1) | AT338512B (en) |
BR (1) | BR7505050A (en) |
CA (1) | CA1046492A (en) |
DK (1) | DK152760C (en) |
FI (1) | FI59107C (en) |
NO (1) | NO148292C (en) |
PH (1) | PH13975A (en) |
PL (1) | PL106505B1 (en) |
SE (1) | SE430787B (en) |
SU (1) | SU1168095A3 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
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IT1054410B (en) * | 1975-11-21 | 1981-11-10 | Mitsui Petrochemical Ind | CATALYSTS FOR THE POLYMERIZATION OF ALPHA OLEFINS |
JPS52100596A (en) * | 1976-02-19 | 1977-08-23 | Mitsui Petrochem Ind Ltd | Production of olefin |
JPS53143684A (en) * | 1977-05-20 | 1978-12-14 | Mitsui Petrochem Ind Ltd | Polymerization of olefin |
JPS5436409U (en) * | 1977-08-17 | 1979-03-09 | ||
US6777508B1 (en) | 1980-08-13 | 2004-08-17 | Basell Poliolefine Italia S.P.A. | Catalysts for the polymerization of olefins |
IT1209255B (en) | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
JPS58113209A (en) * | 1981-12-28 | 1983-07-06 | Nippon Oil Co Ltd | Manufacture of polyolefin |
JPS58113210A (en) * | 1981-12-28 | 1983-07-06 | Nippon Oil Co Ltd | Manufacture of polyolefin |
KR100341040B1 (en) | 1994-08-18 | 2002-11-23 | 칫소가부시키가이샤 | High Rigidity Propylene-Ethylene Block Copolymer Composition and Its Manufacturing Method |
JP3355864B2 (en) * | 1995-04-24 | 2002-12-09 | チッソ株式会社 | Continuous production of high-rigidity propylene / ethylene block copolymer |
JP3765278B2 (en) * | 2002-03-11 | 2006-04-12 | 東邦キャタリスト株式会社 | Solid catalyst component and catalyst for olefin polymerization |
JP2007039529A (en) * | 2005-08-02 | 2007-02-15 | Toho Catalyst Co Ltd | Solid catalytic component for polymerizing olefins, catalyst and method for polymerizing olefin polymers using the same |
SG2014001325A (en) * | 2013-05-21 | 2014-12-30 | China Petroleum & Chemical | A supported nonmetallocene catalyst, preparation and use thereof |
WO2018124070A1 (en) | 2016-12-27 | 2018-07-05 | 三井化学株式会社 | Lubricating oil composition, viscosity modifier for lubricating oil, and additive composition for lubricating oil |
US11873462B2 (en) | 2019-08-29 | 2024-01-16 | Mitsui Chemicals, Inc. | Lubricating oil composition |
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NL7114641A (en) * | 1970-10-29 | 1972-05-03 | ||
GB1452314A (en) * | 1972-11-10 | 1976-10-13 | Mitsui Petrochemical Ind Ld | Catalyst compositions for use in the polymerziation of olefins |
-
1974
- 1974-08-10 JP JP49091181A patent/JPS5120297A/en active Granted
-
1975
- 1975-01-31 CA CA219,139A patent/CA1046492A/en not_active Expired
- 1975-02-03 AT AT77275A patent/AT338512B/en not_active IP Right Cessation
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- 1975-07-30 FI FI752175A patent/FI59107C/en not_active IP Right Cessation
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- 1975-08-07 BR BR7505050*A patent/BR7505050A/en unknown
- 1975-08-08 SU SU752163117A patent/SU1168095A3/en active
- 1975-08-08 SE SE7508961A patent/SE430787B/en not_active IP Right Cessation
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JPS5120297A (en) | 1976-02-18 |
DK152760C (en) | 1988-10-24 |
ATA77275A (en) | 1976-12-15 |
SE430787B (en) | 1983-12-12 |
NO148292C (en) | 1983-09-14 |
PH13975A (en) | 1980-11-20 |
AT338512B (en) | 1977-08-25 |
FI59107C (en) | 1981-06-10 |
SE7508961L (en) | 1976-02-11 |
NO752784L (en) | 1976-02-11 |
CA1046492A (en) | 1979-01-16 |
FI752175A (en) | 1976-02-11 |
BR7505050A (en) | 1976-08-03 |
DK361475A (en) | 1976-02-11 |
PL106505B1 (en) | 1979-12-31 |
SU1168095A3 (en) | 1985-07-15 |
DK152760B (en) | 1988-05-09 |
JPS5236913B2 (en) | 1977-09-19 |
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