NO159282B - Polymeriseringskatalysator, og katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren. - Google Patents
Polymeriseringskatalysator, og katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren. Download PDFInfo
- Publication number
- NO159282B NO159282B NO812675A NO812675A NO159282B NO 159282 B NO159282 B NO 159282B NO 812675 A NO812675 A NO 812675A NO 812675 A NO812675 A NO 812675A NO 159282 B NO159282 B NO 159282B
- Authority
- NO
- Norway
- Prior art keywords
- carbon atoms
- group
- groups
- catalyst
- component
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 32
- 230000000379 polymerizing effect Effects 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims description 36
- 150000002148 esters Chemical class 0.000 claims description 23
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000011949 solid catalyst Substances 0.000 claims description 15
- 150000003377 silicon compounds Chemical class 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000005690 diesters Chemical class 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 claims 1
- 239000011777 magnesium Substances 0.000 description 36
- 239000010936 titanium Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N anhydrous n-heptane Natural products CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- -1 magnesium halide Chemical class 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000005843 halogen group Chemical group 0.000 description 7
- 238000002083 X-ray spectrum Methods 0.000 description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical group CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 230000002140 halogenating effect Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N (2-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940052296 esters of benzoic acid for local anesthesia Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- IQBLWPLYPNOTJC-FPLPWBNLSA-N (z)-4-(2-ethylhexoxy)-4-oxobut-2-enoic acid Chemical compound CCCCC(CC)COC(=O)\C=C/C(O)=O IQBLWPLYPNOTJC-FPLPWBNLSA-N 0.000 description 1
- POXXQVSKWJPZNO-UHFFFAOYSA-N 1-o-ethyl 2-o-(2-methylpropyl) benzene-1,2-dicarboxylate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC(C)C POXXQVSKWJPZNO-UHFFFAOYSA-N 0.000 description 1
- DNILADDSKWDIJH-UHFFFAOYSA-N 2,5-bis(2-methylpropyl)furan-3,4-dicarboxylic acid Chemical compound CC(C)CC=1OC(CC(C)C)=C(C(O)=O)C=1C(O)=O DNILADDSKWDIJH-UHFFFAOYSA-N 0.000 description 1
- CUEJHYHGUMAGBP-UHFFFAOYSA-N 2-[2-(1h-indol-5-yl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1C1=CC=C(NC=C2)C2=C1 CUEJHYHGUMAGBP-UHFFFAOYSA-N 0.000 description 1
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- JEABIFHLYSDNRJ-UHFFFAOYSA-N 2-o-butyl 1-o-ethyl benzene-1,2-dicarboxylate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC JEABIFHLYSDNRJ-UHFFFAOYSA-N 0.000 description 1
- VNLHKIQPMYCHDF-UHFFFAOYSA-N 2-oxopropyl 2-hydroxybenzoate Chemical compound CC(=O)COC(=O)C1=CC=CC=C1O VNLHKIQPMYCHDF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KBESESLMNJYGTQ-UHFFFAOYSA-J Cc1cccc(C)c1O[Ti](Cl)(Cl)Cl Chemical compound Cc1cccc(C)c1O[Ti](Cl)(Cl)Cl KBESESLMNJYGTQ-UHFFFAOYSA-J 0.000 description 1
- RDOFJDLLWVCMRU-UHFFFAOYSA-N Diisobutyl adipate Chemical compound CC(C)COC(=O)CCCCC(=O)OCC(C)C RDOFJDLLWVCMRU-UHFFFAOYSA-N 0.000 description 1
- 229910004721 HSiCl3 Inorganic materials 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 235000012093 Myrtus ugni Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 244000061461 Tema Species 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GZDPONITMCBDOX-UHFFFAOYSA-N [ethoxy(diphenyl)silyl] triethyl silicate Chemical compound C=1C=CC=CC=1[Si](OCC)(O[Si](OCC)(OCC)OCC)C1=CC=CC=C1 GZDPONITMCBDOX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GAHSOBODSWGWHR-UHFFFAOYSA-N bis(2,2-dimethylpropyl) benzene-1,2-dicarboxylate Chemical class CC(C)(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)(C)C GAHSOBODSWGWHR-UHFFFAOYSA-N 0.000 description 1
- ROPXFXOUUANXRR-BUHFOSPRSA-N bis(2-ethylhexyl) (e)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C\C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-BUHFOSPRSA-N 0.000 description 1
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 description 1
- LEYKSONZGURWNL-UHFFFAOYSA-N chloro-diethoxy-phenylsilane Chemical compound CCO[Si](Cl)(OCC)C1=CC=CC=C1 LEYKSONZGURWNL-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- NIXFNZVGGMZGPZ-UHFFFAOYSA-N diethyl 2,2-bis(2-methylpropyl)propanedioate Chemical compound CCOC(=O)C(CC(C)C)(CC(C)C)C(=O)OCC NIXFNZVGGMZGPZ-UHFFFAOYSA-N 0.000 description 1
- RPNFNBGRHCUORR-UHFFFAOYSA-N diethyl 2-butylpropanedioate Chemical compound CCCCC(C(=O)OCC)C(=O)OCC RPNFNBGRHCUORR-UHFFFAOYSA-N 0.000 description 1
- ZTUZDYWYNQDJKR-UHFFFAOYSA-N diethyl cyclohexane-1,2-dicarboxylate Chemical compound CCOC(=O)C1CCCCC1C(=O)OCC ZTUZDYWYNQDJKR-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- FGYDHYCFHBSNPE-UHFFFAOYSA-N diethyl phenylmalonate Chemical compound CCOC(=O)C(C(=O)OCC)C1=CC=CC=C1 FGYDHYCFHBSNPE-UHFFFAOYSA-N 0.000 description 1
- 229940031769 diisobutyl adipate Drugs 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- HHEIMYAXCOIQCJ-UHFFFAOYSA-N ethyl 2,2-dimethylpropanoate Chemical compound CCOC(=O)C(C)(C)C HHEIMYAXCOIQCJ-UHFFFAOYSA-N 0.000 description 1
- YCNSGSUGQPDYTK-UHFFFAOYSA-N ethyl phenyl carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1 YCNSGSUGQPDYTK-UHFFFAOYSA-N 0.000 description 1
- 229940005667 ethyl salicylate Drugs 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- CNWUDMDXRVLRRB-UHFFFAOYSA-N n-[diethoxy(phenyl)silyl]-n-ethylethanamine Chemical compound CCO[Si](OCC)(N(CC)CC)C1=CC=CC=C1 CNWUDMDXRVLRRB-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 125000005546 pivalic acid group Chemical group 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- YYPIRAZPRGBECO-UHFFFAOYSA-N triethoxysilyl acetate Chemical compound CCO[Si](OCC)(OCC)OC(C)=O YYPIRAZPRGBECO-UHFFFAOYSA-N 0.000 description 1
- GYTROFMCUJZKNA-UHFFFAOYSA-N triethyl triethoxysilyl silicate Chemical compound CCO[Si](OCC)(OCC)O[Si](OCC)(OCC)OCC GYTROFMCUJZKNA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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Description
Foreliggende oppfinnelse vedrører katalysatorer av den art
som er angitt i krav l's ingress for polymerisering av cx-olef iner.
De bårede og meget aktive og meget stereospesifikke katalysatorer som til nå har vært anvendt for polymerisering av propylen og høyere olefiner erholdes ved omsetning av en Al-alkyl-forbindelse, delvis kompleksbundet med en elektrondonor-forbindelse (ekstern donor) med en fast forbindelse omfatt-
ende en Ti-forbindelse og en elektrondonor-forbindelse
(intern donor) båret på et magnesiumhalogenid i aktiv form.
Eksempler på slike katalysatorer er beskrevet bl.a. i brit-
isk patent nr. 1,559,194 og belgisk patent nr. 868,682.
Eksterne donorer bestående av silisiumforbindelser inneholdende Si-O-C-bindinger er også beskrevet (japansk patentsøk-
nad Sho 79/94590 og Sho 80/36203). Blant de mange interne donorer er forbindelser som metylmetakrylat og etylpivalat nevnt. Imidlertid i alle de kjente katalysatorer hvori en silisiumforbindelse inneholdende Si-O-C-bindinger har vært anvendt som ekstern donor, har estere av benzosyre og deri-vater derav vært anvendt som intern donor.
Effektiviteten av de ovenfor nevnte katalysatorer, uttrykt
som aktivitet og stereospesifisitet er ikke forskjellige fra effektiviteten av de katalysatorer hvori etylbenzoat og lignende estere av benzosyre har vært anvendt som ekstern donor.
Det er nå overraskende funnet at det er mulig å forøke akti-viteten og stereospesifisiteten for de tidligere kjente bår-
ede katalysatorer omfattende som ekstern donor en silisiumforbindelse inneholdende Si-O-C bindinger, ved å anvende som intern donor en ester med en spesiell struktur.
Katalysatorene ifølge oppfinnelsen omfatter reaksjonsprodukt-
er med de følgende bestanddeler:
a) en Al-trialkyl-forbindelse
b) en silisiumforbindelse inneholdende en eller flere Si-OR-bindinger, hvori R er en hydrokarbongruppe, fortrinnsvis et fenyldi- eller trialkoksysilan eller et alkyldi- ellertrialkoksysilan, og c) en fast bestanddel omfattende et vannfritt Mg-dihalogenid i aktiv form, som bærer, og båret på Mg-dihalogenidet et
Ti-halogenid og en elektrondonorforbindelse, katalysatoren er særpreget ved det som er angitt i krav l's karakteri-serende del, nemlig: at elektrondonorforbindelsen er
1.1) en mono- eller polyester av en mettet dikarboksylsyre hvori minst en av esterkarbonylgruppene er forbundet til et tertiært eller kvarternært karbohatom eller til en forgrenet eller uforgrenet kjede på minst 4 karbonatomer,
1.2) en mono- eller diester av en umettet, polykarboksylsyre hvori 2 karboksygrupper er forbundet med to nabo-karbonatomer som danner en dobbelbinding og hvori hydrokarbongruppen R i COOR-gruppen er en forgrenet mettet eller umettet ålkyl-gruppe med 3-20 karbonatomer, eller er en aryl- eller arylalkylgruppe med 6-20 karbonatomer,
1.3) en mono- eller diester av aromatiske dikarboksylsyre med en COOH-gruppe i ortostillingen hvori minst en av hydrokarbongruppene i COOR-gruppene inneholder 3-20 karbonatomer,
1.4) en mono- eller polyester av hydroksybenzen inneholdende minst 2 hydroksylgrupper i orto-stilling,
1.5) en ester av en mettet eller umettet karboksylsyre med formelen RCOOR' hvori minst en av R og R' er en mettet forgrenet hydrokarbongruppe inneholdende 3-20 karbonatomer, eller er en aryl-alkyl-gruppe med 7-20 karbonatomer, eller er en acylgruppe med 3-20 karbonatomer, eller
1.6) en ester med formelen
hvori minst en av R-gruppene, som kan være like eller forskjellige er en fenylgruppe.
Ytterligere vedrører oppfinnelsen en katalysatorbestanddel
som angitt i krav 2.
Representative estere som er egnet ved fremstilling av komponent c) er som følger:
Klasse 1)
dietyl-diisobutylmalonat, dietyl-n-butylmalonat, dietyl-n-dibutylmalonat, dietylfenylmalonat, dietyl-1,2-cykloheksan-dikarboksylat, dioktylsebacat, diisobutyl-adipat.
Klasse 2)
di-2-etyl-heksyl-maleat, diisobutylmaleat, diisobutyl-3,4-furan-dikarboksylat, di-2-etylheksylfumarat, 2-etylheksyl-monomaleat.
Klasse 3)
diisobutyl-2,3-naftalen,dikarboksylat, di-n-propyl, di-n-
butyl, diisobutyl, di-n-heptyl, di-2-etyl-heksyl, di-n-oktyl, di-neopentil-ftalater, monobutyl- og monoisobutylestere av ftalsyre, etyl-isobutyl-ftalat, etyl-n-butyl-ftalat.
Klasse 4)
1,2-diacetoksybenzen, l-metyl-2,3-diacetoksybenzen.
Klasse 5)
Benzoyl-etylsalicylat, acetyl-metylsalicylat.
Klasse 6)
fenyl-etylkarbonat, difenyl-karbonat.
Foretrukne forbindelser er esterne av malein- pivalin- meta-kryl-, karbon- og ftalsyre.
Ved fremstilling av komponent c) bringes estrene i kontakt med det aktive Mg-dihalogenid eller forløpere for slike dihalogenider som forformede forbindelser eller estrene kan dannes in situ ved hjelp av kjente reaksjoner, f.eks. ved forestring av en alkohol eller et alkoholat og et aryl-halogenid eller av et anhydrid eller en hemiester av en polykarboksylsyre med en alkohol eller ved transforestring. Estrene kan også anvendes i blanding med andre kjente interne donorer.
De aktive vannfrie Mg-dihalogenider danner i det vesentlige en bærer for komponenten c) og er Mg-dihalogenider som i et røntgenpulverspektrum for komponenten c) utviser en spredning (a broadening) på minst 30 % av den mest intense diffraksjonslinje som er tilstede i pulverspektrumet for det tilsvarende dihalogenid med et overflateareale pa 1 m 2 /.g eller er Mg-dihalogenider som utviser et røntgenpulverspek-trum hvori den mest intense diffraksjonslinje er erstattet med en halo hvor intensitetstoppen er forskjøvet i forhold til den interplanare avstand for den mest intense linje og/ eller er Mg dihalogenider med et overflateareale større enn 3 m<2>/g.
Måling av overflatearealet for Mg-dihalogenidene gjøres for komponent c) etter behandling med kokende TiCl^ i 2 h. Den funnede verdi betraktes som overflateareale for Mg-dihalog-. genidet.
Meget aktive former av Mg-dihalogenidene er de som viser røntgenpulverspektrum hvori den mest intense diffraksjonslinje som finnes i spektret for det tilsvarende dihalogenid med et overflateareale på o 1 m 2/g har avtatt i relativ intensitet, og er spredd til å gi en halo, eller de hvori den mest intense linje er erstattet av en halo hvis intensitets-topp er forskjøvet med hensyn til den interplanare avstand til den mest intense linje. Generelt er overflatearealet for de mest aktive former større enn 30 - 40 m 2/g og ligger fortrinnsvis i området 100 - 300 m 2/g.
Aktive former er også de som er avledet fra de ovenfor nevnte former ved varmebehandling av komponent c) i inerte hydrokarbon-oppløsningsmidler og hvis røntgenstrålespektrum viser skarpe diffraksjonslinjer i stedet for halo'er. Den skarpe og mest intense linje for disse former viser en utspredning på minst 30 % i forhold til den tilsvarende linje for Mg dihalogenidet med et overflateareale på 1 m 2/g. Foretrukne Mg-dihalogenider er Mg-diklorid og Mg-dibromid. Vanninn-holdet i dihalogenidene er generelt mindre enn 1 vekt-%.
For Ti-halogenider eller Ti-halogenalkoholater og estere båret på det aktive Mg-dihalogenid er ment de ovenfor nevnte forbindelser som kan være kjemisk eller fysikalsk bundet til bæreren og som ikke er ekstraherbar fra bestanddel c) ved behandling av denne med 1,2-dikloretan i 2 h.
Komponentene a), b) og c) bringes til å reagere med hverandre i en hvilken som helst rekkefølge imidlertid forblandes bestanddelene a) og b) før de bringes i kontakt med komponent c).
Komponent c) kan være forblandet med enten komponent a) og/eller b). Forblanding av a) og b) utføres ved temperaturer som ligger mellom romtemperatur og temperaturen som anvendes ved polymerisasjonsprosessen.
Forreaksjonen mellom c) og b) kan utføres også ved høyere temperatur. Komponent b) kan også innarbeides eller bringes til å reagere med selve komponent c).
Komponent b) bringes til å reagere i et molart forhold i forhold til den halogenerte Ti-forbindelse båret på komponent c) på minst 1 og i et molforhold med hensyn til Al-alkyl-forbindelsen anvendt som komponent a) på minst 20 og fortrinnsvis i området 0,05 - 0,3.
I komponent c) ligger molforholdet mellom Mg-dihalogenidet og den halogenerte Ti-forbindelse som er båret derpå i området 1 - 500 og molforholdet mellom den halogenerte Ti-forbindelse og elektrondonoren båret på Mg-dihalogenidet i området 0,1 - 50. Silikonforbindelsen som inngår i b) innbefatter forbindelser med den generelle formel:
hvori:
R er en alkyl-, alkenyl-, aryl-, arylalkyl- eller cykloalkyl-
gruppe med 1-20 karbonatomer,
Y er -OR', -OCOR', -NR2' hvori R' enten er lik eller forskjellig fra R og har den samme betydning som R,
X er enten halogen eller hydrogen eller en OCOR", ~"NR2" gruppe,
hvori R" enten er lik eller forskjellig fra R' og har
samme betydning som R<1>,
m, n og p er tall som henholdsvis betyr:
m=0-3, n = 1 - 4 og p = 0 - 1 med det forbehold at
m+n+p = 4 .
Andre silisiumforbindelser som kan anvendes er forbindelser hvori 2 eller flere silisiumatomer er bundet til hverandre via oksygen- eller nitrogenatomer. Eksempler på disse forbindelser er heksaetoksydisiloksan, symmetriske difenyl-tetraetoksydisiloksan
Foretrukne silisiumforbindelser er fenylalkoksysilaner så som fenyltrietoksy- eller trimetoksysilan, difenyldimetoksy-og dietoksysilan, monoklorfenyldietoksysilan, alkylalkoksy-silaner så som etyltrietoksysilan, etyltriisopropoksy-silan.
Eksempler på egnede andre forbindelser er klortrietoksy— silan, acetoksytrietoksysilan, vinyltrietokcysilan, butyl-trietoksysilan, trifenylmonoetoksysilan, fenyltricykloetoksy-silan, fenyldietoksydietylaminosilan, tetrafenoksysilan eller tetralkoksysilaner som tetrametoksysilan.
Silisiumforbindelsen kan også dannes in situ ved eksempelvis omsetning av en halogenert silisiumforbindelse så som SiCl4 med en alkohol eller et alkoholat av Mg eller Al.
I katalysatoren i henhold til oppfinnelsen er silisiumforbindelsen tilstede i en kombinert form i det faste produkt av reaksjonen mellom de forskjellige katalysatordannende komponenter idet molforholdet mellom silisiumforbindelsen og den halogenerte Ti-forbindelse er større enn 0,05 og ligger generelt i området 0,1 - 5.
Al-alkylforbindelsen som utgjør bestanddelen a) innbefatter Al-trialkyler eksempelvis Al-trietyl, Al-triisobutyl, Al-triisopropyl og forbindelser inneholdende to eller flére Al-atomer forbundet med hverandre via heteroatomer, så som:
så sorrf:
Som indikert er Al-alkylforbindelser hvori Al-atomene er forbundet via grupper så som SO^ eller SO^ også egnet.
Al-alkylforbindelsene kan anvendes i blanding med Al-alkyl-halogenider så som AlEt^Cl.
Komponent c) fremstilles i henhold til kjente metoder hvor-av en består i å sammale Mg-halogenidet og elektrondonorforbindelsen ifølge foreliggende oppfinnelse inntil frem-komsten av røntgenspekteret for det malte produkt utviser de ovenfor angitte forandringer for Mg-dihalogenidet og deretter omsettas det malte produkt med Ti-forbindelsen.
Fremstillinger av denne type er beskrevet i britisk patent nr. 1.559.194.
Lignende fremstillinger er beskrevet i US-patentene nr. 4.107.413, 4.107.414 og 4.107.415.
En annen metode består i å omsette adduktet av et Mg-halogenid med en alkohol med en Ti-forbindelse i nærvær av en elektrondonorforbindelse som ikke inneholder aktive hydro-genatomer. Denne fremgangsmåte er beskrevet i belgisk patent nr. 868.682.
I henhold til en annen metode som er beskrevet i DOS 3.022.738 så omsettes adduktet mellom Mg-dihalogenidet og alkoholen i væskeform med den halogenerte Ti-forbindelse og elektrondonorforbindelsen.
Ytterligere fremgangsmåter er beskrevet i DOS nr. 2.924.029, US-patent 4.220.554 så vel som i italiensk patentsøknad nr.
27.261/79..
En annen metode omfatter sammaling av Mg-dihalogenidet, den halogenerte Ti-forbindelse og elektrondonorforbindelsen inntil aktivering av Mg-dihalogenidet og deretter behandle det malte produkt i suspensjon i et halogenert hydrokarbon så som 1,2-dikloretan, klorbenzen, metylenklorid og heksakloretan.
Behandlingen utføres ved en temperatur i området fra 4 0°C og kokepunktet for det halogenerte hydrokarbon i et tidsrom på 1 - 4 h.
I henhold til en annen metode impregneres en porøs bærer
så som Si02 eller A^O^, med et lavt innhold av OH-grupper, (fortrinnsvis mindre enn 1 vekt-%) med et flytende addukt mellom Mg-dihalogenidet og en alkohol hvoretter bæreren be-handles med et overskudd av TiCl^ inneholdende oppløst elektrondonorforbindelse ifølge fremgangsmåten beskrevet i tysk patentsøknad nr. 3.022.738 eller belgisk patent nr. 868.682.
Sluttproduktet fremstilt i henhold til de ovenfor nevnte metoder inneholder Mg-dihalogenidet tilstede i en aktiv form, slik som angitt ovenfor.
Andre kjente metoder som fører til dannelse av Mg-dihalogenidet i aktiv form eller til Ti-inneholdende Mg-dihalogenid-bårede komponenter hvori dihalogenidet er tilstede i aktiv form er basert på de følgende reaksjoner: - omsetning av et Grignard-reagens med en Mg R2~forbindelse (R er en hydrokarbylgruppe) eller komplekser av Mg R2~forbindelser med Al-trialkyler, med halogeneringsmidler så som AlX3 eller Al Rmxn forbindelser (X er halogen, R er
en hydrokarbylgruppe, m+n = 3), SiCl^ eller HSiCl3,
- ved omsetning av et Grignard-reagens med en silanol eller polysiloksan, H20 eller med en alkohol og ytterligere omsetning med et halogeneringsmiddel eller med TiCl^, - ved omsetning av Mg med en alkohol og en halogenhydrogen-syre eller Mg med en hydrokarbylhalogenid og en alkohol,
- ved omsetning av MgO med Cl^ eller AlCl^,
- ved omsetning av MgX2-nH20 (X = halogen) med et halogeneringsmiddel eller TiCl^, - eller ved omsetning av Mg mono- eller dialkoholater eller Mg-karboksylater med et halogeneringsmiddel.
Ti-halogenidene eller Ti-halogenalkoholatene innbefatter særlig Ti-tetrahalogenider, Ti-trihalogenider og Ti-tri-halogenalkoholater. Foretrukne forbindelser er: TiCl^, TiBr^/ 2,6-dimetylfenoksytriklortitan.
Ti-trihalogenidene erholdes i henhold til kjente fremgangsmåter, eksempelvis ved reduksjon av TiCl^ med Al eller en metallorganisk Al-forbindelse eller med hydrogen.
For tilfellet Ti-trihalogenider kan det være passende i den hensikt å forbedre effektiviteten av katalysatoren å utføre en oksydasjon, eventuelt partiell, av titanet enten under eller etter fremstillingen av komponent c).
For dette formål kan det anvendes halogener, jodhalogenider.
Foretrukne katalysatorer er de hvori komponent c) er erholdt fra MgC^z TiCl^ og estere av malein-, pivalin- og ftalsyrer og hvori komponent b) er fenyl- eller etyltrietoksysilan eller difenyldimetoksy- eller dietoksysilan.
Komponent a) er en Al-trialkyl så som Al-trietyl eller Al-triisobutyl.
Komponent c) kan fremstilles i henhold til metodene beskrevet i britisk patent nr. 1.559.194, belgisk patent nr. 868.682, tysk patentsøknad nr. 2.924.029, US-patent nr. 4.220.554, italiensk patentsøknad nr. 27.261/79 eller tysk patentsøknad nr. 3.022.738.
Den foretrukne fremgangsmåte ved fremstilling av komponent
c) innbefatter også sammaling av MgCl2, TiCl^ og esteren og deretter behandle det malte produkt med en halogenert hydro-
karbon så som 1,2-dikloretan.
Katalysatoren i henhold til oppfinnelsen anvendes for polymerisering av a-olefiner i henhold til kjente metoder, dvs. ved utføring av polymerisasjonen i væskefase, enten i nærvær eller fravær av et inert hydrokarbonoppløsningsmiddel, eller i gassfase eller eksempelvis kombinering av væskefase-polymerisasjonstrinn etterfulgt av et gassfasepolymerisa-sjonstrinn.
Generelt ligger temperaturen i området 40° - 160°C, fortrinnsvis i området 60° - 90°C idet det arbeides ved atmos-færetrykk eller høyere.
Som molekylvektregulerende bestanddel kan hydrogen eller andre kjente regulatorer anvendes.
Katalysatoren er spesielt egnet ved polymerisering av propylen, buten-1, styren, 4-metylpenten. Katalysatoren kan også anvendes i henhold til kjente metoder for polymerisering av blandinger av propylen og etylen til å gi modifiser-te polypropylener med bedre sjokkmotstandsevne ved lavere temperaturer (såkalte blokkopolymerer av propylen og etylen) eller for erholdelse av tilfeldige krystallinske kopolymer-er av propylen med mindre andeler av etylen.
De følgende eksempler illustrerer oppfinnelsen nærmere.
EKSEMPLENE 1- 10
I en rustfri stålautoklav med et totalvolum på 3 1 og for-synt med magnetisk rører og varmestabilisert ved 6 0°C ved hjelp av et termoelement og holdt under en nitrogenatmosfære, ble det innført 1000 ml av en suspensjon i avgasset og vann-fri n-heptan inneholdende 5 m mol trietylaluminium, fenyltri-etoksysilan (PES) og en fast katalysatorbestanddel fremstilt i henhold til eksempel 1, i italiensk patentsøknad nr. 27.261/79, idet det i steden for etylbenzoat ble anvendt estrene angitt i den etterfølgende tabell I under en samtidig innmatning av propylen. Katalysatorbestanddelene som således ble fremstilt utviste røntgenpulverspektra hvori den mest intense diffraksjonslinje som fremkommer i spekteret for MgCl2 med et overflateareale på 1 ni /g avtar i relativ intensitet og utbrer seg til å danne en halo.
Etter lukking av autoklaven ble hydrogen innført til et trykk på 0,2 kp/cm<2> og temperaturen ble hevet til 70°C og samtidig ble propylen innført til et totaltrykk på 7 kp/cm 2.
Under polymerisasjonen ble trykket holdt konstant ved konti-nuerlig innmatning av monomeren. Etter 4 h ble polymerisasjonen stoppet ved en rask avkjøling og avgassing av poly-meroppslemningen. Polymeren ble separert fra oppløsnings-midlet ved filtrering og tørket i en varm hitrogenstrøm ved 7 0°C. Mengden av polymer oppløst i filtratet ble deretter isolert, veiet og summert til polymerandelen som var oppløs-elig i kokende n-hepta.n, for beregning av isotaktisitets-indeksen (I.I.).
Mengden av den anvendte katalysatorbestanddel og innholdet av Ti i komponenten, molforholdet mellom fenyltrietoksysil-an med hensyn til trietylaluminium, polymerutbytte i forhold til innført katalytisk bestanddel, isotaktisitetsin-deksen (I. I.) , overf lateareale av den faste katalytiske bestanddel og grenseverdien bestemt i tetralin ved 13 5°C er angitt i den etterfølgende tabell I.
EKSEMPEL 11
Eksempel 8 ble gjentatt under de samme polymerisasjonsbe-tingelser som beskrevet i eksemplene 1 - 10, men under anvendelse av den faste katalysatorbestanddel fremstilt i henhold til eksempel 7 i tysk patentsøknad nr. 2.643.143.
Den katalytiske bestanddel viste et røntgenpulverspektrum hvori den mest intense diffraksjonslinje som er tilstede i spekteret for MgCl^ med et overf lateareale på 1 ,m 2/g hadde avtatt i relativ intensitet og spredd seg ut til en halo.
Innholdet av Ti i den faste katalysatorbestanddel, mengden av denne bestanddel, molforholdet mellom trietylaluminium og PES og resultatene av polymerisasj>onsforsøket er vist i tabell I.
EKSEMPEL 12
Den faste katalysatorbestanddel fremstilt i henhold til eksempel 11 ble suspendert i det inerte hydrokarbonoppløs-ningsmiddel "Isopar G" (en blanding av isoparafinhydrokar-boner kokende i området 158° - 172,5°C) og varmebehandlet ved 120°C i 24 h. Den således erholdte katalysatorbestanddel utviste et røntgenspektrum hvori den mest intense diffraksjonslinje som fremkommer som en skarp linje, hvis mid-lere halvtopp-bredde hadde utbredt seg mer enn 3 0 % enn den tilsvarende halvtopp-bredde for MgCl0 med et overflateare-2
ale på lm /g.
Katalysatorbestanddelen ble anvendt under de samme polymeri-sas jonsbetingelser som beskrevet i eksempel 11.
Egenskapene for den faste katalysatorbestanddel, polymerisa-sjonsresultatet er angitt i tabell I.
SAMMENLIGNINGSEKSEMPLER 1 OG 2
Eksempel 1 ble gjentatt under anvendelse av den faste katalysatorbestanddel fremstilt i henhold til eksempel 1 i italiensk patentsøknad nr. 27,261/79. Røntgenpulverspektret var tilsvarende det for katalysatorbestanddelen ifølge eksempel 1. Resultatene av polymerisasjonsforsøkene er gjengitt i tabell I.
SAMMENLIGNINGSEKSEMPEL 3
Eksempel 11 ble gjentatt bortsett fra at den faste katalysatorbestanddel fremstilt i henhold til eksempel 7 i tysk patentsøknad nr. 2.643.143 ble anvendt. Røntgenpulver-spekteret var tilsvarende det for den katalytiske bestanddel ifølge eksempel 11. Resultatene av polymerisasjons-t forsøkene er gjengitt i tabell I.
EKSEMPLENE 13- 18
Eksempel 1 ble gjentatt under anvendelse av en fast katalysatorbestanddel fremstilt på følgende måte: Vannfri MgCl2# en ester som angitt i tabell II og TiCl4 i molforholdet 1:1 med hensyn til esteren ble sammalt i en vibrerende mølle av type "VIBRATOM" (N.V. TEMA'S Gravenhage (Holland)), med et totalvolum på 1 1 og inneholdende 3 kg rustfrie stålkuler med en diameter på 16 mm.
En fyllingskoeffisient lik 100 g/l av det totale volum (vakuum). Møllens indre temperatur var 2 5°C og maletiden var 72 h.
Ifylling av møllen, maling og uttømming av møllen ble fore-tatt under en nitrogenatmosfære. 10 g av det sammalte produkt ble brakt i kontakt med 100 ml 1,2-dikloretan ved 80°C i 2 h, hvoretter 1,2-dikloretan ble fjernet ved filtrering ved 80°C og det gjenværende fast-stoff ble gjentatte ganger vasket med n-heptan ved romtemperatur inntil filtratet var fritt for klorioner og ble deretter oppbevart i form av en heptansuspensjon.
De således fremstilte katalysatorkomponenter viste et rønt-genpulverspektrum hvori den mest intense diffraksjonslinje som fremkommer i spekteret for MgCl„ med et overflateareale på 1 m 2/g hadde avtatt i relativ intensitet og spredd seg til å gi en halo.
Esteren, karakteristika for den faste katalysatorbestanddel
og resultatene av polymerisasjonsforsøkene er vist i tabell
II-
EKSEMPLENE 19- 26
Eksempel 1 ble gjentatt under anvendelse av en fast katalysatorbestanddel fremstilt i henhold til eksempel 3 i italiensk patentsøknad nr. 26.908 A/78.
Et fast addukt MgCl2.2.5 C2H5OH i form av sfæriske partik-
ler ble langsomt tilsatt i en suspensjon av et addukt TiCl^-ester under anvendelse av molforholdende Mg/ester på
10 og TiCl4/C2H5OH på 10.
Blandingen ble deretter oppvarmet til 100°C og holdt ved denne temperatur i 2 h og deretter filtrert ved 100°C. Det resulterende faste produkt ble behandlet med 110 ml TiCl^
ved 120°C i 2 h. Etter denne tidsperiode ble TiCl4 fjernet ved filtrering og faststoffet vasket med n-heptan ved temperaturer synkende fra 90°C til romtemperatur inntil fritt for klorioner og oppbevart i en heptanoppløsning.
Den fremstilte katalysatorbestanddel viste det samme rønt-genspektrum som katalysatorbestanddelen i henhold til eksr emplene 1-10.
Esterne, egenskapene for den faste katalysatorbestanddel og resultatene av polymeriseringsforsøk er gjengitt i tabell
III.
SAMMENLIGNINGSEKSEMPEL 4
Eksempel 19 ble gjentatt, idet det ble anvendt den faste katalysatorbestanddel fremstilt i henhold til eksempel 3
i italiensk patentsøknad nr. 26.908 A/78. Røntgenspekteret for katalysatorbestanddelen var tilsvarende de for eksemp-
lene 1-10. Egenskapene for det faste produkt og resultatet av polymerisasjonsforsøket er gjengitt i tabell III.
EKSEMPLENE 2 7- 29
Eksempel 1 ble gjentatt men under anvendelse av den faste katalysatorbestanddel fremstilt i henhold til eksempel 1
i tysk patentsøknad nr. 3.022.7 38 hvori det istedenfor etylbenzoat ble anvendt estere av ftalsyre som er angitt i tabell IV, som var behandlet med TiCl^ ved 120°C.
Røntgenspekteret for katalysatorbestanddelene var tilsvarende de i henhold til eksemplene 1-10.
Type ester og forhold er angitt i tabell IV.
Arbeidsbetingelsene og resultatene av polymerisasjonsforsøk er gjengitt i tabell IV.
SAMMENLIGNINGSEKSEMPEL 5
Eksempel 27 ble gjentatt men under anvendelse av den faste katalysatorbestanddel fremstilt i henhold til eksempel 1
i tysk patentsøknad nr. 3.022.738.
Arbeidsbetingelsene og resultatet av polymerisasjonsforsøk-et er vist i tabell 3.
EKSEMPLENE 30- 34
Eksempel 8 ble gjentatt bortsett fra istedenfor fenyltriet-oksysilan ble anvendt en ekvimolar mengde av de alkoksysil-aner som er vist i tabell V.
Egenskapene for katalysatorbestanddelen og resultatet av polymerisasjonsforsøkene er gjengitt i tabell V.
Claims (2)
1. Katalysator for polymerisering av o<-olefiner, som består av et reaksjonsprodukt av de følgende bestanddeler: a) en Al-trialkylforbindelse, b) en silisiumforbindelse inneholdende en eller flere Si-OR-bindinger, hvori R er1 en hydrokarbongruppe, fortrinnsvis et fenyJdi- eller trialkoksysilan eller et alkyldi- eller trialkoksysilan, og c) en fast bestanddel omfattende et vannfritt Mg-dihalogenid i aktiv form, som bærer og båret på Mg-dihalogenidet et Ti-halogenid og en elektrondonorforbindelse, karakterisert ved at elektrondonorforbindelsen er
1.1 en mono- eller polyester av en mettet dikarboksylsyre hvori minst en av esterkarbonylgruppene er forbundet til et tertiært eller kvarternært karbonatom eller til en forgrenet eller uforgrenet kjede på minst 4 karbonatomer ,
1.2 en mono- eller diester av en umettet dikarboksylsyre hvori 2 karboksylgrupper er forbundet med tc nabokar-bonatomer som danner en dobbeltbinding og hvori hydrokarbongruppen R i -COCR-gruppen er en forgrenet mettet eller umettet alkylgruppe med 3-20 karbonatomer, eller er en aryl- eller arylalkylgruppe med 6-20 karbonatomer,
1.3 en mono- eller diester av en aromatisk dikarboksylsyre med en COOH-gruppe i orto-stillingen hvori minst en av hydrokarbongruppene i COCR-gruppene inneholder 3-20 karbonatomer,
1.4 en mono- eller polyestere av et hyc.i oksybenzen inne-holdene minst 2 hydroksylgrupper i orto-stillingen, 1.5 en ester av en mettet eller umettet karboksylsyre med
formelen RCOOR' hvori minst en av R og R' er en mettet eller umettet forgrenethydrokarbongruppe inneholdende 3-20 karbonatomer, eller er en aryl-alkyl-gruppe med 7-20 karbonatomer, eller en acylgruppe med 3-20 karbonatomer, eller 1.6 en ester med formelen
hvori minst en av R-gruppene, som kan være like eller forskjellige, er en fenylgruppe.
2. Fast katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren i henhold til krav 1, karakterisert ved at den består av den faste bestanddel c) i krav 1, hvor Mg-dihalogenidet er Mg-diklorid eller Mg-dibromid, Ti-halogenidet er et Ti-tetra-halogenid og esteren er valgt fra gruppene 1.2, 1.3, 1.5 og 1.6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT8024141A IT1209255B (it) | 1980-08-13 | 1980-08-13 | Catalizzatori per la polimerizzazione di olefine. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| NO812675L NO812675L (no) | 1982-02-15 |
| NO159282B true NO159282B (no) | 1988-09-05 |
| NO159282C NO159282C (no) | 1988-12-14 |
Family
ID=11212191
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO812677A NO159283C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, og fast katalysatorbestanddelfor anvendelse ved fremstilling av katalysatoren. |
| NO812675A NO159282C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, og katalysatorbestanddel for anvendelse ved fremstilling av katalysatoren. |
| NO812676A NO160303C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, katalysatorbestanddel for fremstilling av katalysatoren og anvendelse av katalysatoren. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO812677A NO159283C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, og fast katalysatorbestanddelfor anvendelse ved fremstilling av katalysatoren. |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO812676A NO160303C (no) | 1980-08-13 | 1981-08-06 | Polymeriseringskatalysator, katalysatorbestanddel for fremstilling av katalysatoren og anvendelse av katalysatoren. |
Country Status (27)
| Country | Link |
|---|---|
| US (4) | US6515085B1 (no) |
| EP (4) | EP0045977B2 (no) |
| JP (11) | JPS5763310A (no) |
| KR (3) | KR840000803B1 (no) |
| AR (1) | AR244254A1 (no) |
| AT (4) | ATE42311T1 (no) |
| AU (3) | AU559388B2 (no) |
| BR (3) | BR8105185A (no) |
| CA (3) | CA1185961A (no) |
| CS (2) | CS226436B2 (no) |
| DE (4) | DE3177032D1 (no) |
| DK (3) | DK163248C (no) |
| ES (3) | ES8300794A1 (no) |
| FI (3) | FI70030C (no) |
| HU (3) | HU186399B (no) |
| IN (3) | IN155867B (no) |
| IT (1) | IT1209255B (no) |
| MX (3) | MX159065A (no) |
| NO (3) | NO159283C (no) |
| PH (3) | PH17748A (no) |
| PL (3) | PL140239B1 (no) |
| PT (3) | PT73499B (no) |
| RU (1) | RU2111975C1 (no) |
| SG (1) | SG33087G (no) |
| SU (2) | SU1457813A3 (no) |
| YU (3) | YU42419B (no) |
| ZA (3) | ZA815496B (no) |
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| JPS588690B2 (ja) * | 1978-07-14 | 1983-02-17 | 出光興産株式会社 | ポリエチレンの製造方法 |
| JPS5919566B2 (ja) | 1978-07-28 | 1984-05-07 | 東亜燃料工業株式会社 | α−オレフイン重合用触媒成分の製造方法 |
| IT1098272B (it) | 1978-08-22 | 1985-09-07 | Montedison Spa | Componenti,di catalizzatori e catalizzatori per la polimerizzazione delle alfa-olefine |
| JPS5534238A (en) * | 1978-08-31 | 1980-03-10 | Chisso Corp | Preparation of alpha-olefin polymer |
| JPS6011924B2 (ja) * | 1978-09-05 | 1985-03-29 | 旭化成株式会社 | オレフイン重合用触媒 |
| US4331558A (en) | 1978-12-11 | 1982-05-25 | Phillips Petroleum Company | Polymerization catalyst and process |
| US4243552A (en) * | 1978-12-11 | 1981-01-06 | Phillips Petroleum Company | Polymerization catalyst and process |
| AU529558B2 (en) | 1978-12-20 | 1983-06-09 | Consortium Fur Elektrochemische Industrie Gmbh | Agglomereted mixtures of metel oxides |
| EP0014523B1 (en) | 1979-01-10 | 1983-03-30 | Imperial Chemical Industries Plc | Olefine polymerisation catalyst and the production and use thereof |
| JPS55102606A (en) * | 1979-01-30 | 1980-08-06 | Mitsui Toatsu Chem Inc | Polymerization of alpha-olefin |
| PL118176B1 (en) | 1979-02-20 | 1981-09-30 | Zaklady Chem Oswiecim | Process for manufacturing surface-active agent |
| JPS55123604A (en) * | 1979-03-17 | 1980-09-24 | Toyo Soda Mfg Co Ltd | Preparation of polyolefin |
| JPS55135105A (en) | 1979-04-10 | 1980-10-21 | Mitsui Petrochem Ind Ltd | Titanium catalyst component for olefin polymerization |
| DE3064564D1 (en) | 1979-04-30 | 1983-09-22 | Shell Int Research | Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions |
| JPS55145706A (en) * | 1979-05-01 | 1980-11-13 | Mitsui Toatsu Chem Inc | Polymerization of alpha-olefine |
| CA1141093A (en) | 1979-05-17 | 1983-02-08 | Brian L. Goodall | Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions |
| JPS56811A (en) | 1979-06-18 | 1981-01-07 | Mitsui Petrochem Ind Ltd | Preparation of olefin polymer or copolymer |
| JPS5626902A (en) | 1979-08-09 | 1981-03-16 | Denki Kagaku Kogyo Kk | Polymerization of olefin |
| JPS5634707A (en) * | 1979-08-30 | 1981-04-07 | Toa Nenryo Kogyo Kk | Alpha-olefin polymerization catalyst component, and its use |
| IT1127222B (it) | 1979-11-14 | 1986-05-21 | Montedison Spa | Componenti di catalizzatori per la polimerizzazione di olefine |
| JPS56126026A (en) * | 1980-03-05 | 1981-10-02 | Hideo Inui | Bending method and its die device |
| JPS56126029A (en) * | 1980-03-06 | 1981-10-02 | Natl House Ind Co Ltd | Die device for drawing |
| JPS56125405A (en) | 1980-03-07 | 1981-10-01 | Mitsui Petrochem Ind Ltd | Treatment of olefin polymer |
| JPS56126027A (en) * | 1980-03-07 | 1981-10-02 | Toshiba Corp | Method for changing bending r of u-bender |
| JPS56126025A (en) * | 1980-03-10 | 1981-10-02 | Hitachi Metals Ltd | Cold roll forming method |
| IT1209255B (it) | 1980-08-13 | 1989-07-16 | Montedison Spa | Catalizzatori per la polimerizzazione di olefine. |
| IT1190683B (it) | 1982-02-12 | 1988-02-24 | Montedison Spa | Componenti e catalizzatori per la polimerizzazione di olefine |
| JPS59117509A (ja) | 1982-12-24 | 1984-07-06 | Mitsui Petrochem Ind Ltd | オレフインの重合方法 |
-
1980
- 1980-08-13 IT IT8024141A patent/IT1209255B/it active
-
1981
- 1981-08-06 DK DK349881A patent/DK163248C/da not_active IP Right Cessation
- 1981-08-06 NO NO812677A patent/NO159283C/no unknown
- 1981-08-06 DK DK349681A patent/DK160256C/da not_active IP Right Cessation
- 1981-08-06 FI FI812442A patent/FI70030C/fi not_active IP Right Cessation
- 1981-08-06 FI FI812440A patent/FI70028C/fi not_active IP Right Cessation
- 1981-08-06 DK DK349781A patent/DK164878C/da active
- 1981-08-06 NO NO812675A patent/NO159282C/no unknown
- 1981-08-06 NO NO812676A patent/NO160303C/no unknown
- 1981-08-06 FI FI812441A patent/FI70029C/fi not_active IP Right Cessation
- 1981-08-07 PH PH26023A patent/PH17748A/en unknown
- 1981-08-07 PH PH26024A patent/PH17763A/en unknown
- 1981-08-07 PH PH26022A patent/PH17760A/en unknown
- 1981-08-07 SU SU813389099A patent/SU1457813A3/ru active
- 1981-08-10 PT PT73499A patent/PT73499B/pt unknown
- 1981-08-10 ZA ZA815496A patent/ZA815496B/xx unknown
- 1981-08-10 ZA ZA815487A patent/ZA815487B/xx unknown
- 1981-08-10 ZA ZA815491A patent/ZA815491B/xx unknown
- 1981-08-10 PT PT73501A patent/PT73501A/pt unknown
- 1981-08-10 PT PT73500A patent/PT73500A/pt unknown
- 1981-08-11 AU AU73971/81A patent/AU559388B2/en not_active Expired
- 1981-08-11 PL PL1981232576A patent/PL140239B1/pl unknown
- 1981-08-11 IN IN893/CAL/81A patent/IN155867B/en unknown
- 1981-08-11 IN IN892/CAL/81A patent/IN154898B/en unknown
- 1981-08-11 PL PL1981232574A patent/PL139915B1/pl unknown
- 1981-08-11 AU AU73973/81A patent/AU557334B2/en not_active Expired
- 1981-08-11 PL PL1981232575A patent/PL140238B1/pl unknown
- 1981-08-11 AR AR81286397A patent/AR244254A1/es active
- 1981-08-11 AU AU73972/81A patent/AU552621B2/en not_active Expired
- 1981-08-11 IN IN894/CAL/81A patent/IN154219B/en unknown
- 1981-08-12 CS CS816045A patent/CS226436B2/cs unknown
- 1981-08-12 CA CA000383700A patent/CA1185961A/en not_active Expired
- 1981-08-12 CS CS816046A patent/CS226437B2/cs unknown
- 1981-08-12 YU YU1959/81A patent/YU42419B/xx unknown
- 1981-08-12 SU SU813450787A patent/SU1568890A3/ru active
- 1981-08-12 HU HU812342A patent/HU186399B/hu unknown
- 1981-08-12 BR BR8105185A patent/BR8105185A/pt unknown
- 1981-08-12 HU HU812342A patent/HU186400B/hu unknown
- 1981-08-12 HU HU812341A patent/HU186397B/hu unknown
- 1981-08-12 MX MX188710A patent/MX159065A/es unknown
- 1981-08-12 YU YU1957/81A patent/YU42579B/xx unknown
- 1981-08-12 CA CA000383709A patent/CA1174225A/en not_active Expired
- 1981-08-12 YU YU1958/81A patent/YU42418B/xx unknown
- 1981-08-12 MX MX188711A patent/MX159151A/es unknown
- 1981-08-12 ES ES504715A patent/ES8300794A1/es not_active Expired
- 1981-08-12 ES ES504716A patent/ES8300795A1/es not_active Expired
- 1981-08-12 RU SU3397401A patent/RU2111975C1/ru active
- 1981-08-12 ES ES504717A patent/ES8300796A1/es not_active Expired
- 1981-08-12 CA CA000383747A patent/CA1185960A/en not_active Expired
- 1981-08-12 BR BR8105190A patent/BR8105190A/pt unknown
- 1981-08-12 BR BR8105189A patent/BR8105189A/pt unknown
- 1981-08-12 MX MX188712A patent/MX159066A/es unknown
- 1981-08-13 EP EP81106301A patent/EP0045977B2/en not_active Expired - Lifetime
- 1981-08-13 AT AT81106299T patent/ATE42311T1/de not_active IP Right Cessation
- 1981-08-13 AT AT86112847T patent/ATE68794T1/de active
- 1981-08-13 EP EP86112847A patent/EP0223010B1/en not_active Expired - Lifetime
- 1981-08-13 JP JP56126025A patent/JPS5763310A/ja active Granted
- 1981-08-13 DE DE8181106299T patent/DE3177032D1/de not_active Expired
- 1981-08-13 JP JP56126026A patent/JPS5763311A/ja active Granted
- 1981-08-13 DE DE8181106300T patent/DE3177124D1/de not_active Expired
- 1981-08-13 KR KR1019810002943A patent/KR840000803B1/ko not_active Expired
- 1981-08-13 DE DE8686112847T patent/DE3177262D1/de not_active Expired - Lifetime
- 1981-08-13 KR KR1019810002944A patent/KR840000804B1/ko not_active Expired
- 1981-08-13 AT AT81106301T patent/ATE24731T1/de not_active IP Right Cessation
- 1981-08-13 DE DE8181106301T patent/DE3175804D1/de not_active Expired
- 1981-08-13 EP EP81106299A patent/EP0045975B1/en not_active Expired
- 1981-08-13 JP JP56126027A patent/JPS5763312A/ja active Granted
- 1981-08-13 KR KR1019810002942A patent/KR840000802B1/ko not_active Expired
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- 1981-08-13 AT AT81106300T patent/ATE48144T1/de not_active IP Right Cessation
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1987
- 1987-04-10 SG SG330/87A patent/SG33087G/en unknown
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1990
- 1990-08-20 JP JP2217248A patent/JPH03115310A/ja active Granted
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1991
- 1991-06-18 JP JP3171823A patent/JPH0670097B2/ja not_active Expired - Lifetime
- 1991-06-18 JP JP3171844A patent/JPH075662B2/ja not_active Expired - Lifetime
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1994
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- 1994-01-31 JP JP6025986A patent/JP2500298B2/ja not_active Expired - Lifetime
- 1994-07-05 JP JP6174845A patent/JP2647626B2/ja not_active Expired - Lifetime
- 1994-07-05 JP JP6174844A patent/JP2647625B2/ja not_active Expired - Lifetime
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1995
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- 1995-06-06 US US08/469,734 patent/US5618771A/en not_active Ceased
- 1995-06-06 US US08/469,735 patent/US6194342B1/en not_active Expired - Lifetime
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1996
- 1996-07-29 JP JP8214949A patent/JP2749799B2/ja not_active Expired - Lifetime
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