JPS6320443B2 - - Google Patents
Info
- Publication number
- JPS6320443B2 JPS6320443B2 JP1092382A JP1092382A JPS6320443B2 JP S6320443 B2 JPS6320443 B2 JP S6320443B2 JP 1092382 A JP1092382 A JP 1092382A JP 1092382 A JP1092382 A JP 1092382A JP S6320443 B2 JPS6320443 B2 JP S6320443B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- butadiene
- cis
- polybutadiene
- hexane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 64
- 238000006116 polymerization reaction Methods 0.000 claims description 64
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 63
- 238000009835 boiling Methods 0.000 claims description 26
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002685 polymerization catalyst Substances 0.000 claims description 24
- 229920002857 polybutadiene Polymers 0.000 claims description 23
- 239000005062 Polybutadiene Substances 0.000 claims description 22
- 150000001869 cobalt compounds Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- -1 organoaluminium halide Chemical class 0.000 claims description 17
- 150000004820 halides Chemical class 0.000 claims description 14
- 150000002900 organolithium compounds Chemical class 0.000 claims description 11
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229940117953 phenylisothiocyanate Drugs 0.000 claims description 5
- 238000000034 method Methods 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- OAYSYSIGKCDBKZ-UHFFFAOYSA-N 1-isothiocyanato-2-phenylbenzene Chemical compound S=C=NC1=CC=CC=C1C1=CC=CC=C1 OAYSYSIGKCDBKZ-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,Nâdiethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- KYPVLDPQHIDKQJ-UHFFFAOYSA-N cobalt;ethyl 3-oxobutanoate Chemical compound [Co].CCOC(=O)CC(C)=O KYPVLDPQHIDKQJ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- HRGXHRPMGDCKQM-UHFFFAOYSA-L dichlorocobalt;pyridine Chemical class Cl[Co]Cl.C1=CC=NC=C1 HRGXHRPMGDCKQM-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
ãã®çºæã¯ãããªãã¿ãžãšã³ã®æ°èŠãªè£œé æ³ã«
é¢ãããã®ã§ããã
è£åŒ·ããªãã¿ãžãšã³ã®è£œé æ³ãšããŠã¯ãäžæŽ»æ§
ææ©æº¶åªäžã§ãã³ãã«ãååç©ãšäžè¬åŒAlRo
X3-oïŒãã ããã¯ççŽ æ°ïŒãïŒã®ã¢ã«ãã«åºã
ããšãã«åºãŸãã¯ã·ã¯ãã¢ã«ãã«åºã§ãããã¯
ããã²ã³ååã§ãããïœã¯1.5ãïŒã®æ°åã§ããïŒ
ã§è¡šããããããã²ã³å«æææ©ã¢ã«ãããŠã åå
ç©ãšããåŸãããã·ã¹âéå觊åªã®ååšäžã«ã
ïŒïŒïŒâãã¿ãžãšã³ãéåããŠã·ã¹âïŒïŒïŒâã
ãªãã¿ãžãšã³ãçæãããç¶ããŠãã®éåç³»ã«ã
ããã«ïŒïŒïŒâãã¿ãžãšã³ããã³ïŒãŸãã¯åèšæº¶
åªãæ·»å ããããããã¯æ·»å ããªãã§ãã³ãã«ã
ååç©ãšãäžè¬åŒAlR3ïŒãã ããã¯åèšãšåã
ã§ãããïŒã§è¡šããããææ©ã¢ã«ãããŠã ååç©
ãšãäºç¡«åççŽ ãšããåŸãããïŒïŒïŒéå觊åªã
ååšãããŠãïŒïŒïŒâãã¿ãžãšã³ãéåããæ¹æ³
ãå
¬ç¥ã§ããïŒç¹å
¬æ49â17666å·ïŒã
ãããåèšã®æ¹æ³ã¯ïŒïŒïŒâéå觊åªã®ã¢ã«ã
ããŠã æåãšããŠäžè¬åŒAlR3ã§è¡šããããææ©
ã¢ã«ãããŠã ååç©ãçšããæ¹æ³ã§ããã
ããã§ãïŒïŒïŒâéå觊åªã®ã¢ã«ãããŠã æå
ãšããŠãžã¢ã«ãã«ã¢ã«ãããŠã ãã©ã€ããçšãã
æ¹æ³ãææ¡ãããïŒç¹éæ56â88409å·ïŒã
äžèšå
¬å ±ã«ã¯éå溶åªäžã§ãå¯æº¶æ§ã³ãã«ãå
åç©ããã³äžè¬åŒAlR2XïŒïŒ²ã¯ççŽ æ°ïŒãïŒã®ã¢
ã«ãã«åºã§ãããã¯ããã²ã³ååã§ãããïŒã§
è¡šãããããžã¢ã«ãã«ã¢ã«ãããŠã ãã©ã€ããã
ãªãã·ã¹âïŒïŒïŒâéå觊åªã®ååšäžã«ïŒïŒïŒâ
ãã¿ãžãšã³ãéåããŠã·ã¹âïŒïŒïŒâããªãã¿ãž
ãšã³ãçæãããç¶ããŠãã®éåç³»ã«ãããã«
ïŒïŒïŒâãã¿ãžãšã³ããã³ïŒãŸãã¯åèšæº¶åªãæ·»
å ããããããã¯æ·»å ããªãã§ãå¯æº¶æ§ã³ãã«ã
ååç©ããžã¢ã«ãã«ã¢ã«ãããŠã ãã©ã€ããäºç¡«
åççŽ ããã³é»åäŸäžæ§ææ©ååç©ãããªãïŒïŒ
ïŒâéå觊åªãååšãããŠïŒïŒïŒâãã¿ãžãšã³ã
éåããè£åŒ·ããªãã¿ãžãšã³ã®è£œé æ³ãèšèŒãã
ãŠããã
ãããäžèšã®æ¹æ³ã«ãã€ãŠè£œé ãããè£åŒ·ããª
ãã¿ãžãšã³ã¯ã沞隰ïœâãããµã³äžæº¶åã®èç¹ã
188ã198âïŒå®æœäŸã«ããïŒãšæ¯èŒçäœãã
ãã®çºæè
ãã¯ãææ©ã¢ã«ãããŠã ååç©ãšã
ãŠææ©ã¢ã«ãããŠã ãã©ã€ãã䜿çšããŠã沞隰ïœ
âãããµã³äžæº¶åã®èç¹ã200â以äžã§ããè£åŒ·
ããªãã¿ãžãšã³ã補é ããæ¹æ³ã«ã€ããŠç 究ãã
çµæããã®çºæãå®æããã
ããªãã¡ããã®çºæã¯ãïŒïŒïŒâãã¿ãžãšã³ã®
éå溶åªæº¶æ¶²äžã§ãå¯æº¶æ§ã³ãã«ãååç©ããã³
ææ©ã¢ã«ãããŠã ãã©ã€ããããªãã·ã¹âïŒïŒïŒ
éå觊åªã®ååšäžã«ïŒïŒïŒâãã¿ãžãšã³ãéåã
ãŠã·ã¹âïŒïŒïŒããªãã¿ãžãšã³ãçæãããç¶ã
ãŠãã®éåç³»ã«å¯æº¶æ§ã³ãã«ãååç©ãææ©ã¢ã«
ãããŠã ãã©ã€ããææ©ãªããŠã ååç©ããã³äº
ç¡«åççŽ ãããã¯ã€ãœããªã·ã¢ã³é
žããšãã«ãã
ãªãïŒïŒïŒâéå觊åªãååšãããŠïŒïŒïŒâãã¿
ãžãšã³ãéåããŠã沞隰ïœâãããµã³äžæº¶åãïŒ
ã30ïŒ
ã沞隰ïœâãããµã³å¯æº¶åã95ã70ïŒ
ã§ã
ãæçµããªãã¿ãžãšã³ãçæãããããšãç¹åŸŽãš
ããè£åŒ·ããªãã¿ãžãšã³ã®è£œé æ³ã«é¢ãããã®ã§
ããããã®çºæã®è£œé æ³ã第ïŒå³ã«ç€ºãã
ãã®çºæã®æ¹æ³ã«ãããŠãã·ã¹âïŒïŒïŒâéå
觊åªã®ã³ãã«ãæåã§ããå¯æº¶æ§ã³ãã«ãååç©
ã¯ã䜿çšããéå溶åªã«å¯æº¶ãªã³ãã«ãååç©ã§
ããã°ã©ã®ãããªãã®ã§ããããäŸãã°ããã®ã
ããªå¯æº¶æ§ã®ã³ãã«ãååç©ãšããŠã¯ãã³ãã«ã
ã®Î²âãžã±ãã³é¯äœãŸãã¯ã³ãã«ãã®Î²âã±ãé
ž
ãšã¹ãã«é¯äœã奜é©ã«äœ¿çšãããããããã³ãã«
ãé¯äœã®é
äœåã®Î²âãžã±ãã³ãšããŠã¯ãäžè¬åŒ
ïŒåŒäžãR1ããã³R2ã®ããããã¯ãæ°ŽçŽ ååãŸ
ãã¯ççŽ æ°ïŒãïŒã®èèªæçåæ°ŽçŽ åºã§ããã
R3ããã³R4ã®ããããã¯ççŽ æ°ïŒãïŒã®èèªæ
çåæ°ŽçŽ åºã§ãããïŒã®Î²âãžã±ãã³é¡ãããã
ãããŸããé
äœåã®Î²âã±ãé
žãšã¹ãã«ãšããŠ
ã¯ãäžè¬åŒ
ïŒåŒäžãR1ãR2ãR3ããã³R4ã¯åèšãšåãã§ã
ããïŒã®Î²âã±ãé
žãšã¹ãã«ãããããããç¹ã«
奜ãŸããé¯äœã¯ãã³ãã«ã()ã¢ã»ãã«ã¢ã»ãã
ãŒããã³ãã«ã()ã¢ã»ãã«ã¢ã»ãããŒããã³ã
ã«ãã¢ã»ãé
¢é
žãšãã«ãšã¹ãã«é¯äœã§ããã
ãŸãå¯æº¶æ§ã®ã³ãã«ãååç©ãšããŠãççŽ æ°ïŒ
以äžã®ææ©ã«ã«ãã³é
žã®ã³ãã«ãå¡©ãäŸãã°ã³ã
ã«ããªã¯ããšãŒããã³ãã«ããããããŒããã³ã
ã«ããã³ãŸãšãŒããªã©ã䜿çšããããšãã§ããã
ããã«ãå¯æº¶æ§ã®ã³ãã«ãååç©ãšããŠãäŸã
ã°ããã²ã³åã³ãã«ãé¯äœãããªãã¡äžè¬åŒ
CoXnã»Ym (3)
ïŒåŒäžãã¯ããã²ã³ååãç¹ã«å¥œãŸããã¯å¡©çŽ
ååã§ãããïœã¯ïŒãŸãã¯ïŒã®æŽæ°ã§ãããã¯
é
äœåã§ãããïœã¯ïŒãïŒã®æŽæ°ã§ãããïŒã§è¡š
ããããé¯äœã奜é©ã«äœ¿çšããããšãã§ãããäž
åŒ(3)ã«ãããŠãé
äœåãšããŠã¯ããã²ã³åã³ãã«
ããšé¯äœã圢æããããšãç¥ãããŠããä»»æã®é
äœåãäŸãã°ããªãžã³ãããªãšãã«ã¢ãã³ãããª
ããã«ã¢ãã³ããžã¡ãã«ã¢ããªã³ãªã©ã®ã¢ãã³ã
ã¡ãã«ã¢ã«ã³ãŒã«ããšãã«ã¢ã«ã³ãŒã«ãªã©ã®ã¢ã«
ã³ãŒã«ããã³ïŒ®ïŒïŒ®âãžã¡ãã«ãã«ã ã¢ããã
ïŒïŒ®âãžã¡ãã«ã¢ã»ãã¢ãããïŒïŒ®âãžãšã
ã«ãã«ã ã¢ãããªã©ã®ïŒ®ïŒïŒ®âãžã¢ã«ãã«ã¢ãã
ãªã©ãæããããšãã§ãããç¹ã«å¥œãŸããããã²
ã³åã³ãã«ãé¯äœãšããŠã¯ãå¡©åã³ãã«ãããªãž
ã³é¯äœãå¡©åã³ãã«ããšãã«ã¢ã«ã³ãŒã«é¯äœãæ
ããããšãã§ããã
ãã®çºæã®æ¹æ³ã«ãããŠãã·ã¹âïŒïŒïŒâéå
觊åªã®ã¢ã«ãããŠã æåã§ããææ©ã¢ã«ãããŠã
ãã©ã€ãã¯ãäžè¬åŒAlRoX3-oïŒãã ããã¯ççŽ
æ°ïŒãïŒã®ã¢ã«ãã«åºãããšãã«åºãŸãã¯ã·ã¯ã
ã¢ã«ãã«åºã§ãããã¯ããã²ã³ååã§ãããïœ
ã¯1.5ãïŒã®æ°åã§ããïŒã§è¡šããããååç©ã§
ãããææ©ã¢ã«ãããŠã ãã©ã€ããšããŠããžãšã
ã«ã¢ã«ãããŠã ã¢ãã¯ãã©ã€ãããžãšãã«ã¢ã«ã
ããŠã ã¢ãããã©ã€ãããžã€ãœããã«ã¢ã«ãããŠ
ã ã¢ãã¯ãã©ã€ããªã©ã®ãžã¢ã«ãã«ã¢ã«ãããŠã
ãã©ã€ããããšãã«ã¢ã«ãããŠã ã»ã¹ãã¯ãã©ã€
ãã®ãããªã¢ã«ãã«ã¢ã«ãããŠã ã»ã¹ããã©ã€ã
ãªã©ã奜é©ã«äœ¿çšããããšãã§ããã
ã·ã¹âïŒïŒïŒéå觊åªã®äœ¿çšéã¯ãïŒïŒïŒâã
ã¿ãžãšã³ïŒã¢ã«ã«å¯ŸããŠãå¯æº¶æ§ã³ãã«ãååç©
ã0.005ããªã¢ã«ä»¥äžãç¹ã«0.01ããªã¢ã«ä»¥äžã§
ãããææ©ã¢ã«ãããŠã ãã©ã€ãã0.5ããªã¢ã«
以äžãç¹ã«ïŒããªã¢ã«ä»¥äžã§ããããšã奜ãŸã
ãããŸããå¯æº¶æ§ã³ãã«ãååç©ã«å¯Ÿããææ©ã¢
ã«ãããŠã ãã©ã€ãã®ã¢ã«æ¯ïŒAlïŒCoïŒã¯ïŒä»¥
äžãç¹ã«15以äžã§ããããšã奜ãŸããã
ïŒïŒïŒâãã¿ãžãšã³ã®éå溶åªæº¶æ¶²çšã®éå溶
åªãšããŠã¯ã圢æãããã·ã¹âïŒïŒïŒâããªãã¿
ãžãšã³ã溶解ãããææ©æº¶åªã§ããã°ç¹ã«å¶éã¯
ãªããããã³ãŒã³ããã«ãšã³ããã·ã¬ã³ãªã©ã®è³
éŠæçåæ°ŽçŽ ãïœâããã¿ã³ãïœâãããµã³ãªã©
ã®èèªæçåæ°ŽçŽ ãã·ã¯ããããµã³ãªã©ã®èç°æ
çåæ°ŽçŽ ããã³ãããã®ããã²ã³åç©ãäŸãã°ã¯
ãã«ãã³ãŒã³ãâãžã¯ãã«ãã³ãŒã³ãå¡©åã¡ã
ã¬ã³ãïŒïŒïŒâãžã¯ãã«ãšã¿ã³ãïŒïŒïŒïŒïŒâã
ãªã¯ãã«ãšã¿ã³ãªã©ãæããããšãã§ãããïŒïŒ
ïŒâãã¿ãžãšã³ã®éå溶åªæº¶æ¶²äžã®æ°Žåã®éã¯50
mgïŒïŒppmïŒä»¥äžãç¹ã«10ã50mgïŒã奜ãŸã
ãã
ãã®çºæã®æ¹æ³ã«ãããã·ã¹âïŒïŒïŒâéåã®
éå枩床ã¯â20ã80âãç¹ã«20ã70âã奜ãŸã
ããéåå§åã¯åžžå§ã§ããã以äžã§ããããéå
æéã¯10åãïŒæéã®ç¯å²ã奜ãŸããããŸããå
å¿ç³»ã«ãããïŒïŒïŒâãã¿ãžãšã³ã®ã·ã¹âïŒïŒïŒ
âéåæã®æ¿åºŠã¯å
šéå溶液ã«å¯ŸããŠïŒã40éé
ïŒ
ã®ç¯å²ã§ããã°ããã
åèšã®ã·ã¹âïŒïŒïŒâéåã¯ãã·ã¹âïŒïŒïŒâ
æ§é å«æç90ïŒ
以äžãç¹ã«95ïŒ
以äžã§ãåºæç²åºŠ
ãηãïŒãã«ãšã³äžã30âã§æž¬å®ïŒãïŒãïŒãç¹ã«
1.3ãïŒã§ããã·ã¹âïŒïŒïŒâããªãã¿ãžãšã³ã
çæããããã«è¡ãã®ã奜ãŸãããåºæç²åºŠãé©
åœãªå€ã«ããçºã«ãå
¬ç¥ã®ååé調ç¯å€ãäŸã
ã°ãã·ã¯ããªã¯ã¿ãžãšã³ïŒä»¥åŸCODãšç¥èšã
ãïŒãã¢ã¬ã³ãªã©ã®éå
±åœ¹ãžãšã³é¡ãŸãã¯Î±âãª
ã¬ãã€ã³é¡ã䜿çšããããšãã§ããã
ãã®çºæã®æ¹æ³ã«ãããŠã¯ãåèšã®ã·ã¹âïŒïŒ
ïŒâéåå·¥çšã§åŸãããã·ã¹âïŒïŒïŒâããªãã¿
ãžãšã³ããã³ã·ã¹âïŒïŒïŒâéå觊åªãå«æãã
éå溶液äžã«ãïŒïŒïŒâéå觊åªãååšãããŠ
ïŒïŒïŒâãã¿ãžãšã³ãïŒïŒïŒâéåãããã®ã§ã
ãã
ïŒïŒïŒâéå觊åªã®ã³ãã«ãæåã§ããå¯æº¶æ§
ã³ãã«ãååç©ã¯ãåèšã®ã·ã¹âïŒïŒïŒâéå觊
åªã®ã³ãã«ãæåãšãŸã€ããåããã®ã䜿çšã§ã
ãã
ïŒïŒïŒâéå觊åªã®ã¢ã«ãããŠã æåã§ããæ
æ©ã¢ã«ãããŠã ãã©ã€ãã¯ãåèšã®ã·ã¹âïŒïŒïŒ
éå觊åªã®ã¢ã«ãããŠã æåãšãŸã€ããåããã®
ã䜿çšã§ããã
ãã®çºæã®æ¹æ³ã«ãããŠäœ¿çšãããïŒïŒïŒâé
å觊åªæåã®ææ©ãªããŠã ååç©ã¯ãã¢ã«ãã«ãª
ããŠã ååç©ãã¢ãªãŒã«ãªããŠã ååç©ãã¢ã«ã
ã¬ã³ãžãªããŠã ååç©ãããã¯ã¢ãªã¬ã³ãžãªããŠ
ã ååç©ã§ãããææ©ãªããŠã ååç©ãšããŠããš
ãã«ãªããŠã ãïœâãããã«ãªããŠã ãã€ãœãã
ãã«ãªããŠã ãïœâããã«ãªããŠã ãsecâãã
ã«ãªããŠã ãtertâããã«ãªããŠã ãã¢ãã«ãªã
ãŠã ãªã©ã®ã¢ã«ãã«ãªããŠã ååç©ã奜é©ã«äœ¿çš
ããããšãã§ããã
ãã®çºæã®æ¹æ³ã«ãããŠã¯ïŒïŒïŒâéå觊åªæ
åãšããŠäºç¡«åççŽ ãããã¯ã€ãœããªã·ã¢ã³é
žã
ãšãã«ã奜ãŸããã¯äºç¡«åççŽ ã䜿çšãããã
ãã®çºæã®æ¹æ³ã«ãããŠã¯ãå¯æº¶æ§ã³ãã«ãå
åç©ãææ©ã¢ã«ãããŠã ãã©ã€ããææ©ãªããŠã
ååç©ããã³äºç¡«åççŽ ãããã¯ã€ãœããªã·ã¢ã³
é
žããšãã«ãããªãïŒæå系觊åªã®ååšäžã«ïŒïŒ
ïŒâãã¿ãžãšã³ãéåããããšãå¿
èŠã§ãããæ
æ©ãªããŠã ååç©ãçšããªãã§ä»ã®ïŒæåãããª
ã觊åªã®ååšäžã«ïŒïŒïŒâãã¿ãžãšã³ãéåããŠ
ããé«èç¹ãé«ååéã®æ²žéš°ïœâãããµã³äžæº¶å
ãæããè£åŒ·ããªãã¿ãžãšã³ãåŸãããšã¯ã§ããª
ãïŒæ¯èŒäŸïŒïŒã
ãã®çºæã®æ¹æ³ã«ãããïŒïŒïŒâéå觊åªåæ
åã®äœ¿çšéã¯éåã«äŸãããïŒïŒïŒâãã¿ãžãšã³
ã«å¯ŸããŠãéå溶åªã«å¯æº¶æ§ã®ã³ãã«ãååç©ã
0.0005ã0.1ã¢ã«ïŒ
ãææ©ã¢ã«ãããŠã ãã©ã€ã
ã0.01ãïŒã¢ã«ïŒ
ãææ©ãªããŠã ååç©ã0.01ã
ïŒã¢ã«ïŒ
ãäºç¡«åççŽ ãããã¯ã€ãœããªã·ã¢ã³é
ž
ããšãã«ã0.001ãïŒã¢ã«ïŒ
ã§ããããšã奜ãŸã
ãããŸããææ©ã¢ã«ãããŠã ãã©ã€ãã®éã¯å¯æº¶
æ§ã³ãã«ãååç©ïŒã¢ã«ã«å¯ŸããŠ10ã500ã¢ã«ã
ç¹ã«20ã200ã¢ã«ã奜ãŸãããææ©ãªããŠã åå
ç©ã®éã¯å¯æº¶æ§ã³ãã«ãååç©ïŒã¢ã«ã«å¯ŸããŠïŒ
ã200ã¢ã«ãç¹ã«10ã100ã¢ã«ã奜ãŸãããäºç¡«å
ççŽ ãããã¯ã€ãœããªã·ã¢ã³é
žããšãã«ã®éã¯å¯
溶æ§ã³ãã«ãååç©ïŒã¢ã«ã«å¯ŸããŠ0.1ã500ã¢
ã«ãç¹ã«ïŒã500ã¢ã«ã奜ãŸããã
ãŸããææ©ãªããŠã ååç©ã®éã¯éåç³»äžã«å
åšããæ°Žåã®éïŒïŒïŒïŒâãã¿ãžãšã³ã®éå溶åª
溶液äžã«ååšããæ°Žåã®éïŒïŒã¢ã«ã«å¯ŸããŠïŒã¢
ã«ä»¥äžã§ããããšã奜ãŸãããæ°Žåãšææ©ã¢ã«ã
ããŠã ãã©ã€ããšã®åèšéã®1.5åã¢ã«ä»¥äžã§ã
ãããšã奜ãŸããã
ãŸããææ©ã¢ã«ãããŠã ãã©ã€ããšããŠäžè¬åŒ
AlR1.5X1.5ïŒïŒ²ãã¯çè¿°ã®ãšããïŒã§è¡šããã
ãååç©ãäŸãã°ããšãã«ã¢ã«ãããŠã ã»ã¹ãã¯
ãã©ã€ããçšããå Žåã«ã¯ãææ©ãªããŠã ååç©
ã®éã¯ææ©ã¢ã«ãããŠã ãã©ã€ãïŒã¢ã«ã«å¯ŸããŠ
0.5ã¢ã«ä»¥äžã§ããããšã奜ãŸããã
ïŒïŒïŒéå觊åªåæåã®æ·»å é åºãæ·»å æ¹æ³ã«
ã¯ç¹ã«å¶éã¯ãªãããäºç¡«åççŽ ãããšãã«ã€ãœ
ããªã·ã¢ã³é
žããšãã«ã®æ·»å é åºã¯åæåã®æåŸ
ã奜ãŸãããããããå®æœäŸïŒã«ç€ºãããã«ã·ã¹
âïŒïŒïŒéåã®åã«ãããããå ããŠããããšã
ã§ããããŸããææ©ãªããŠã ååç©ã¯ããããµ
ã³ããã³ãŒã³ãªã©ã®çåæ°ŽçŽ æº¶åªã®æº¶æ¶²ãšããŠã·
ã¹âïŒïŒïŒéå溶液ã«çŽæ¥å ããããšãã§ããã
ææ©ãªããŠã ååç©ãã·ã¹âïŒïŒïŒéå溶液ã«æ·»
å ããåã«ãïŒïŒïŒâãã¿ãžãšã³ãäºç¡«åççŽ ã
ããšãã«ã€ãœããªãã¢ã³é
žããšãã«ãšæ¥è§Šããã
ãšïŒïŒïŒâéåã®æŽ»æ§ãèãããäœäžããå Žåã
ããã®ã§æ³šæããå¿
èŠãããã
ãã®çºæã®æ¹æ³ã«ãããïŒïŒïŒâéåã®éåæž©
床ã¯â20ã80âãç¹ã«20ã60âã奜ãŸãããéå
å§åã¯åžžå§ã§ããã以äžã§ããããéåæéã¯10
åãïŒæéã®ç¯å²ã奜ãŸããã
ïŒïŒïŒâéåçšã®æº¶åªã¯ã·ã¹âïŒïŒïŒâéå溶
åªãšåæ§ã§ããã
ãã®çºæãå®æœããå Žåã«ã¯ãéåã«äŸãã
ïŒïŒïŒâãã¿ãžãšã³ããã³æº¶åªã®å
šéãã·ã¹â
ïŒïŒïŒâéåå·¥çšã«ãããŠæ·»å ããŠãããããã
ãã¯ãïŒïŒïŒâãã¿ãžãšã³ã®ã·ã¹âïŒïŒïŒâéå
å·¥çšã«ãããŠãïŒïŒïŒâãã¿ãžãšã³ããã³ïŒãŸã
ã¯æº¶åªãäžéšæ·»å ããã€ãã§ïŒïŒïŒâéåå·¥çšã«
ãããŠãïŒïŒïŒâãã¿ãžãšã³ããã³ïŒãŸãã¯æº¶åª
ã®æ®éãæ·»å ããŠãããããã®éåå¿ç³»ã«ããã
ïŒïŒïŒâãã¿ãžãšã³ã®æ¿åºŠã¯å
šéå溶液ã«å¯ŸããŠ
ïŒã40ééïŒ
ã®ç¯å²ã§ããããšã奜ãŸããã
ãŸãããã®çºæã®æ¹æ³ã¯ããããåŒãšããŠåäž
åå¿å®¹åšå
ã§ãã·ã¹âïŒïŒïŒâéåãšããã«ç¶ã
ãŠïŒïŒïŒâéåãšãè¡ãããšã«ãã€ãŠããããã
ã¯é£ç¶æ³ãšããŠãã·ã¹âïŒïŒïŒâéååãšããã
ã«é£ãªãïŒïŒïŒâéååãšã§ïŒïŒïŒâãã¿ãžãšã³
ãé£ç¶çã«éåãããããšã«ãã€ãŠããå·¥æ¥çã«
å®æœã§ããã
ãã®çºæã®æ¹æ³ã«ãããŠã¯ãåèšã®éåã¯ã沞
éš°ïœâãããµã³äžæº¶åãïŒã30ïŒ
ã沞隰ïœâãã
ãµã³å¯æº¶åã95ã70ïŒ
ã§ããæçµããªãã¿ãžãšã³
ãçæãããŸã§è¡ãªãã
éååå¿çµäºåŸããªãã¿ãžãšã³ãååŸããã«ã¯
å
¬ç¥ã®æ¹æ³ãé©çšããããšãã§ãããäŸãã°ãé
ååå¿çµäºåŸãéå溶液ã«ææ©ã¢ã«ãããŠã ãã©
ã€ããšåå¿ãããããªã¢ã«ã³ãŒã«ãæ°Žãªã©ã®æ¥µæ§
溶å€ã倧éæå
¥ããæ¹æ³ããããã¯å€§éã®æ¥µæ§æº¶
å€ã«éå溶液ãæå
¥ããæ¹æ³ãå¡©é
žãç¡«é
žãªã©ã®
ç¡æ©é
žãé
¢é
žãå®æ¯éŠé
žãªã©ã®ææ©é
žãã¢ããšã¿
ããŒã«ã¢ãã³ãã¢ã³ã¢ãã¢ãå«ãå°éã®æ¥µæ§æº¶å€
ãéå溶液ã«æå
¥ããæ¹æ³ãå¡©åæ°ŽçŽ ã¬ã¹ãéå
溶液ã«å°å
¥ããæ¹æ³ãªã©ã«ããïŒïŒïŒâãã¿ãžãš
ã³ã®éåãåæ¢ããåŸãã¡ã¿ããŒã«ãªã©ã®æ²æ®¿å€
ãå ãããããããã¯ãã©ãã·ãŠïŒæ°Žèžæ°ãå¹ã
ããããŸãã¯å¹ãããŸãããŠæº¶åªãèžçºé€å»ã
ãïŒããŠéåäœãæåºãããåé¢åŸä¹Ÿç¥ããŠããª
ãã¿ãžãšã³ãŽã ãåŸãããšãã§ããã
ãã®çºæã®æ¹æ³ã«ãã€ãŠåŸãããããªãã¿ãžãš
ã³ã¯ã沞隰ïœâãããµã³å¯æº¶åãšæ²žéš°ïœâãããµ
ã³äžæº¶åïŒHIïŒãšãããªãã沞隰ïœâãããµã³
äžæº¶åãïŒã30ïŒ
ã§ããã沞隰ïœâãããµã³å¯æº¶
åã95ã70ïŒ
ã§ããã奜é©ã«ã¯ã沞隰ïœâãããµ
ã³å¯æº¶åã¯åºæç²åºŠïŒãηãïŒïŒ30âããã«ãšã³äžæž¬
å®ïŒãïŒãïŒã§ãããã·ã¹âïŒïŒïŒæ§é å«æçã
92ïŒ
以äžã§ããã沞隰ïœâãããµã³äžæº¶åã¯åºæ
ç²åºŠïŒãηãïŒïŒ135âãããã©ãªã³äžæž¬å®ïŒã0.5ã
ïŒã§ãããïŒïŒïŒâæ§é å«æçã85ïŒ
以äžã§ã
ããèç¹ã200ã220âã§ããããããŠããã®æ²žéš°
ïœâãããµã³äžæº¶åã®ïŒïŒïŒâæ§é éšåã¯äž»ãšã
ãŠã·ã³ãžãªã¿ã¯ããã¯âïŒïŒïŒâæ§é ãæããŠã
ãã
ãã®çºæã®æ¹æ³ã«ããåŸãããããªãã¿ãžãšã³
ã¯ãåŸæ¥ã倩ç¶ãŽã ãé«ã·ã¹âïŒïŒïŒâããªãã¿
ãžãšã³ã«çšããããŠããæ¢ç¥ã®é
åå€ãé
åãã
ããšãã§ããã
ãŸãããã®çºæã®æ¹æ³ã«ããåŸãããããªãã¿
ãžãšã³ã倩ç¶ãŽã ãä»ã®åæãŽã ãšãã¬ã³ãããŠ
䜿çšããããšãã§ããã
次ã«å®æœäŸããã³æ¯èŒäŸã瀺ããå®æœäŸããã³
æ¯èŒäŸã®èšèŒã«ãããŠãããªãã¿ãžãšã³ã®æ²žéš°ïœ
âãããµã³äžæº¶åã¯ãïŒïœã®è£åŒ·ããªãã¿ãžãšã³
ã200mlã®ïœâãããµã³ã«å®€æž©ã§æº¶è§£ãããåŸã
äžæº¶åãïŒæéãœã¯ã¹ã¬ãŒæœåºåšã«ãã€ãŠæœåº
ããæœåºæ®åãç空也ç¥ãããã®ééã粟秀ããŠ
æ±ãããã®ã§ããããŸãã沞隰ïœâãããµã³å¯æº¶
åã¯ãäžèšã®ããã«ããŠåŸãããïœâãããµã³æº¶
解åããã³ãœã¯ã¹ã¬ãŒæœåºåšã«ããæœåºåããïœ
âãããµã³ãèžçºé€å»ããåŸãç空也ç¥ãããã®
ééã粟秀ããŠæ±ãããã®ã§ããããŸããè£åŒ·ã
ãªãã¿ãžãšã³ã®æ²žéš°ïœâãããµã³å¯æº¶åããã³ã·
ã¹âïŒïŒïŒéååŸã®ããªãã¿ãžãšã³ã®ã·ã¹âïŒïŒ
ïŒæ§é å«æçã¯èµ€å€åžåã¹ãã¯ãã«ïŒIRïŒã«ã
ã枬å®ãã沞隰ïœâãããµã³äžæº¶åã®ïŒïŒïŒâæ§
é å«æçã¯æ žç£æ°å
±é³Žã¹ãã¯ãã«ïŒNMRïŒã«ã
ã枬å®ãã沞隰ïœâãããµã³äžæº¶åã®èç¹
ïŒMPïŒã¯èªèšå·®åç±éèšïŒDSCïŒã«ããåžç±æ²
ç·ã®ããŒã¯æž©åºŠã«ãã決å®ããã
ãŸããè£åŒ·ããªãã¿ãžãšã³ã®æ²žéš°ïœâãããµã³
å¯æº¶åããã³ã·ã¹âïŒïŒïŒéååŸã®ããªãã¿ãžãš
ã³ã®åºæç²åºŠïŒãηãïŒã«ã€ããŠã¯30âããã«ãšã³
äžã§æž¬å®ããå€ã§ãããè£åŒ·ããªãã¿ãžãšã³ã®æ²ž
éš°ïœâãããµã³äžæº¶åã®åºæç²åºŠïŒãηãïŒã«ã€ã
ãŠã¯135âãããã©ãªã³äžã§æž¬å®ããå€ã§ããã
å®æœäŸ ïŒ
空æ°ãçªçŽ ã§çœ®æãã枩床èšãæ¹ææ£ãçªçŽ ã¬
ã¹å°å
¥ç®¡ãåããå
容ç©ïŒã®ã»ãã©ãã«ãã©ã¹
ã³äžã«ã也ç¥ããïŒïŒïŒâãã¿ãžãšã³85ïœãè±æ°Ž
ãã³ãŒã³860mlã«æº¶è§£ããïŒïŒïŒâãã¿ãžãšã³ã®
ãã³ãŒã³æº¶æ¶²ïŒæ°Žå1.0ããªã¢ã«å«æïŒãå
¥ãã
液枩ã70âã«ä¿ã¡ãªããããã®ïŒïŒïŒâãã¿ãžãš
ã³ã®ãã³ãŒã³æº¶æ¶²ã«ã·ã¯ããªã¯ã¿ãžãšã³4.6ããª
ã¢ã«ããžãšãã«ã¢ã«ãããŠã ã¢ãã¯ãã©ã€ã4.0
ããªã¢ã«ããã³ã³ãã«ããªã¯ããšãŒã0.043ããª
ã¢ã«ãæ¹æããªããé 次添å ããåŸãåŒãç¶ãæ¹
æããªãã40âã§10åéïŒïŒïŒâãã¿ãžãšã³ãã·
ã¹âïŒïŒïŒéåãããããªããŒã¯ã·ã¹âïŒïŒïŒæ§
é å«æçã96ïŒ
以äžã§ããããηãã2.4ã§ãã€ãã
ã·ã¹âïŒïŒïŒéååŸãçŽã¡ã«ïœâããã«ãªããŠã
2.0ããªã¢ã«ããã³äºç¡«åççŽ 0.13ããªã¢ã«ãæ·»
å ããåŸãæ¹æããªãã40âã§ïŒåéïŒïŒïŒâã
ã¿ãžãšã³ãïŒïŒïŒéåãããåŸãããããªããŒç
ææ··åç©ã«å°éã®ïŒïŒïŒâãžç¬¬ïŒããã«âïŒâã¡
ãã«ããšããŒã«ããã³å¡©é
žãå«ãïŒã®ã¡ã¿ããŒ
ã«ãå ãéååå¿ãåæ¢ããããæåºæ²æ®¿ããã
ãªããŒãéããçŽ20âã§æžå§ä¹Ÿç¥ããŠããªãã¿
ãžãšã³50.8ïœãåŸãã
ãã®ããªãã¿ãžãšã³ã¯ã沞隰ïœâãããµã³äžæº¶
åã15.7ïŒ
å«ã¿ã沞隰ïœâãããµã³äžæº¶åã®ïŒïŒ
ïŒâæ§é å«æçã92.0ïŒ
ã§ãããèç¹ã204âã§
ãããåºæç²åºŠïŒãηãïŒã4.0ã§ããã沞隰ïœâã
ããµã³å¯æº¶åã®ã·ã¹âïŒïŒïŒâæ§é å«æçã96.2
ïŒ
ã§ãããåºæç²åºŠïŒãηãïŒïŒãã«ãšã³ã30âïŒã
2.3ã§ãã€ãã
å®æœäŸ ïŒãïŒ
éåæ¡ä»¶ã第ïŒè¡šã®ããã«ãããä»ã¯å®æœäŸïŒ
ãšåæ§ã«è¡ãªã€ããçµæã第ïŒè¡šã«ç€ºãã
This invention relates to a new method for producing polybutadiene. The method for producing reinforced polybutadiene is to combine a cobalt compound with the general formula AlR o in an inert organic solvent.
X 3-o (However, R is an alkyl group having 1 to 6 carbon atoms,
phenyl group or cycloalkyl group, X is a halogen atom, n is a number from 1.5 to 2)
In the presence of a cis-polymerization catalyst obtained from a halogen-containing organoaluminum compound represented by
1,3-butadiene is polymerized to produce cis-1,4-polybutadiene, and then this polymerization system is
Further, a cobalt compound, an organoaluminum compound represented by the general formula AlR 3 (wherein R is the same as above), and a disulfide compound, with or without addition of 1,3-butadiene and/or the above-mentioned solvent, are added. A method of polymerizing 1,3-butadiene in the presence of a 1,2 polymerization catalyst obtained from carbon is known (Japanese Patent Publication No. 17666/1983). However, the above method uses an organoaluminum compound represented by the general formula AlR 3 as the aluminum component of the 1,2-polymerization catalyst. Therefore, a method was proposed in which a dialkyl aluminum halide was used as the aluminum component of the 1,2-polymerization catalyst (Japanese Patent Application Laid-open No. 88409/1983). The above publication describes that in a polymerization solvent, a cis- 1,3- in the presence of a 1,4-polymerization catalyst
Butadiene is polymerized to form cis-1,4-polybutadiene, and then a soluble cobalt compound, a dialkyl aluminum halide is added to the polymerization system with or without further addition of 1,3-butadiene and/or said solvent. , 1 consisting of carbon disulfide and an electron-donating organic compound,
A method for producing reinforced polybutadiene is described in which 1,3-butadiene is polymerized in the presence of a 2-polymerization catalyst. However, the reinforced polybutadiene produced by the above method has a melting point of boiling n-hexane insoluble components.
Relatively low at 188-198°C (depending on the example). The inventors used an organoaluminum halide as the organoaluminum compound to
-This invention was completed as a result of research into a method for producing reinforced polybutadiene whose hexane-insoluble content has a melting point of 200°C or higher. That is, the present invention provides cis-1,4 polymerization consisting of a soluble cobalt compound and an organoaluminum halide in a polymerization solvent solution of 1,3-butadiene.
1,3-butadiene is polymerized in the presence of a polymerization catalyst to produce cis-1,4 polybutadiene, and then a soluble cobalt compound, an organoaluminum halide, an organolithium compound, and carbon disulfide or phenyl isothiocyanate are added to the polymerization system. 1,3-butadiene is polymerized in the presence of a 1,2-polymerization catalyst consisting of
30% and a final polybutadiene having a boiling n-hexane soluble content of 95-70%. The manufacturing method of this invention is shown in FIG. In the method of this invention, the soluble cobalt compound which is the cobalt component of the cis-1,4-polymerization catalyst may be any cobalt compound as long as it is soluble in the polymerization solvent used. For example, as such a soluble cobalt compound, a cobalt β-diketone complex or a cobalt β-keto acid ester complex is preferably used. The β-diketone ligand of these cobalt complexes has the general formula (In the formula, each of R 1 and R 2 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms,
Each of R 3 and R 4 is an aliphatic hydrocarbon group having 1 to 3 carbon atoms. ) β-diketones, and as β-keto acid esters of the ligand, the general formula (In the formula, R 1 , R 2 , R 3 and R 4 are the same as above.) β-keto acid esters are mentioned. Particularly preferred complexes are cobalt () acetylacetonate, cobalt () acetylacetonate, and cobalt acetoacetic acid ethyl ester complex. Also, as a soluble cobalt compound, carbon number 6
Cobalt salts of the above organic carboxylic acids, such as cobalt octoate, cobalt naphthenate, cobalt benzoate, etc., can be used. Furthermore, as a soluble cobalt compound, for example, a halogenated cobalt complex, that is, a general formula CoXn.Ym (3) (wherein, X is a halogen atom, particularly preferably a chlorine atom, and n is an integer of 2 or 3, A complex represented by Y is a ligand and m is an integer of 1 to 4 can also be suitably used. In the above formula (3), the ligand is any ligand known to form a complex with cobalt halide, such as amines such as pyridine, triethylamine, tributylamine, and dimethylaniline;
Alcohols such as methyl alcohol and ethyl alcohol and N,N-dimethylformamide,
Examples include N,N-dialkylamides such as N,N-dimethylacetamide and N,N-diethylformamide. Particularly preferred cobalt halide complexes include cobalt chloride pyridine complexes and cobalt chloride ethyl alcohol complexes. In the method of this invention, the organoaluminum halide that is the aluminum component of the cis-1,4-polymerization catalyst has the general formula AlR o X 3-o (where R is an alkyl group having 1 to 6 carbon atoms, a phenyl group, or is an alkyl group, X is a halogen atom, n
is a number from 1.5 to 2). As the organoaluminum halide, dialkylaluminum halides such as diethylaluminum monochloride, diethylaluminum monobroride, diisobutylaluminum monochloride, and alkylaluminum sesquihalides such as ethylaluminum sesquichloride can be suitably used. The amount of the cis-1,4 polymerization catalyst used is such that the soluble cobalt compound is 0.005 mmol or more, especially 0.01 mmol or more, and the organoaluminum halide is 0.5 mmol or more, especially 1 mmol or more, per 1 mole of 1,3-butadiene. It is preferable that Further, the molar ratio (Al/Co) of the organoaluminium halide to the soluble cobalt compound is preferably 5 or more, particularly 15 or more. The polymerization solvent for the polymerization solvent solution of 1,3-butadiene is not particularly limited as long as it is an organic solvent that can dissolve the formed cis-1,4-polybutadiene, but aromatic solvents such as benzene, toluene, and xylene can be used. Hydrocarbons, aliphatic hydrocarbons such as n-heptane and n-hexane, alicyclic hydrocarbons such as cyclohexane, and their halides, such as chlorobenzene, O-dichlorobenzene, methylene chloride, 1,2-dichloroethane, Examples include 1,1,2-trichloroethane. 1,
The amount of water in the polymerization solvent solution of 3-butadiene is 50
mg/(ppm) or less, particularly preferably 10 to 50 mg/. The polymerization temperature for cis-1,4-polymerization in the method of this invention is preferably -20 to 80°C, particularly 20 to 70°C, the polymerization pressure may be normal pressure or higher, and the polymerization time is 10 minutes to 5 hours. A range is preferred. In addition, cis-1,4 of 1,3-butadiene in the reaction system
-The concentration during polymerization may be in the range of 5 to 40% by weight based on the total polymerization solution. The cis-1,4-polymerization described above is cis-1,4-
The structural content is 90% or more, especially 95% or more, and the intrinsic viscosity [η] (measured in toluene at 30°C) is 1 to 4, especially
It is preferable to carry out the reaction so that cis-1,4-polybutadiene having a molecular weight of 1.3 to 3 is produced. In order to adjust the intrinsic viscosity to a suitable value, known molecular weight regulators, for example, non-conjugated dienes such as cyclooctadiene (hereinafter abbreviated as COD) and allene, or α-olefins can be used. In the method of this invention, the above-mentioned cis-1,
A 1,2-polymerization catalyst is present in a polymerization solution containing cis-1,4-polybutadiene obtained in the 4-polymerization step and a cis-1,4-polymerization catalyst to convert 1,3-butadiene into 1,2-polybutadiene. -It polymerizes. The soluble cobalt compound which is the cobalt component of the 1,2-polymerization catalyst can be exactly the same as the cobalt component of the cis-1,4-polymerization catalyst described above. The organoaluminum halide which is the aluminum component of the 1,2-polymerization catalyst is the above-mentioned cis-1,4
The same aluminum component as the polymerization catalyst can be used. The organolithium compound as a 1,2-polymerization catalyst component used in the method of the present invention is an alkyllithium compound, an aryllithium compound, an alkylene dilithium compound or an allyl dilithium compound. As the organolithium compound, alkyllithium compounds such as ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and amyllithium can be suitably used. In the method of this invention, carbon disulfide or phenyl isothiocyanate, preferably carbon disulfide, is used as the 1,2-polymerization catalyst component. In the method of this invention, 1,
It is necessary to polymerize 3-butadiene. Even if 1,3-butadiene is polymerized in the presence of a catalyst consisting of other three components without using an organolithium compound, it is not possible to obtain reinforced polybutadiene with a high melting point, high molecular weight, and a content insoluble in boiling n-hexane. (Comparative Example 1). The amount of each component of the 1,2-polymerization catalyst used in the method of this invention is such that the cobalt compound soluble in the polymerization solvent is
0.0005 to 0.1 mol%, organoaluminum halide 0.01 to 1 mol%, organolithium compound 0.01 to 1 mol%
Preferably, the amount of carbon disulfide or phenyl isothiocyanate is 0.001 to 1 mol%. In addition, the amount of organoaluminum halide is 10 to 500 mol per 1 mol of soluble cobalt compound,
In particular, 20 to 200 mol is preferable, and the amount of the organolithium compound is 5 to 5 mol per mol of the soluble cobalt compound.
The amount of carbon disulfide or phenyl isothiocyanate is preferably 0.1 to 500 mol, particularly 1 to 500 mol, per mol of the soluble cobalt compound. Further, the amount of the organolithium compound is preferably 1 mol or more per 1 mol of water present in the polymerization system (the amount of water present in the polymerization solvent solution of 1,3-butadiene); The amount is preferably 1.5 times the mole or less of the total amount of the organic aluminum halide and the organic aluminum halide. Also, as an organoaluminum halide, the general formula
When using a compound represented by AlR 1.5 X 1.5 (R,
It is preferably 0.5 mol or more. There are no particular restrictions on the order and method of addition of each component of the 1,2 polymerization catalyst, but the order of addition of carbon disulfide and phenyl phenyl isothiocyanate is preferably at the end of each component. However, as shown in Example 2, it can also be added in advance before cis-1,4 polymerization. Alternatively, the organolithium compound can be added directly to the cis-1,4 polymerization solution as a solution in a hydrocarbon solvent such as hexane or benzene.
Before adding the organolithium compound to the cis-1,4 polymerization solution, 1,3-butadiene, carbon disulfide,
Care must be taken because the 1,2-polymerization activity may be significantly reduced when brought into contact with phenyl phenylisothiothianate. The polymerization temperature for 1,2-polymerization in the method of this invention is preferably -20 to 80°C, particularly 20 to 60°C, the polymerization pressure may be normal pressure or higher, and the polymerization time is 10 to 10°C.
A range of minutes to 5 hours is preferred. The solvent for 1,2-polymerization is the same as the cis-1,4-polymerization solvent. When carrying out this invention, the total amount of 1,3-butadiene and solvent used for polymerization must be reduced to cis-
It may be added in the 1,4-polymerization step, or in the cis-1,4-polymerization step of 1,3-butadiene, part of the 1,3-butadiene and/or solvent may be added, and then the 1,2 - In the polymerization step, the remaining amount of 1,3-butadiene and/or solvent may be added. At this time, the concentration of 1,3-butadiene in the reaction system is preferably in the range of 3 to 40% by weight based on the total polymerization solution. The method of the present invention can also be carried out by carrying out cis-1,4-polymerization and subsequent 1,2-polymerization in the same reaction vessel as a batch method, or by carrying out cis-1,4-polymerization followed by 1,2-polymerization in the same reaction vessel as a batch method, or by carrying out cis-1,4-polymerization followed by 1,2-polymerization as a continuous method. It can also be carried out industrially by continuously polymerizing 1,3-butadiene in a 1,4-polymerization zone and a 1,2-polymerization zone connected thereto. In the process of this invention, the polymerization is carried out until a final polybutadiene is produced having a boiling n-hexane insoluble content of 5 to 30% and a boiling n-hexane soluble content of 95 to 70%. A known method can be applied to obtain polybutadiene after the completion of the polymerization reaction. For example, after the polymerization reaction is complete, a large amount of a polar solvent such as alcohol or water that reacts with organoaluminum halide is added to the polymerization solution, or a large amount of polar solvent is added to the polymerization solution, or an inorganic solvent such as hydrochloric acid or sulfuric acid is added to the polymerization solution. Polymerization of 1,3-butadiene can be carried out by adding a small amount of polar solvent containing acid, organic acids such as acetic acid and benzoic acid, monoethanolamine and ammonia into the polymerization solution, or introducing hydrogen chloride gas into the polymerization solution. After stopping, the polymer is precipitated by adding a precipitating agent such as methanol or by flashing (by blowing in water vapor or not blowing in water to remove the solvent by evaporation), and after separation, it is dried to obtain polybutadiene rubber. be able to. The polybutadiene obtained by the method of this invention consists of a boiling n-hexane soluble fraction and a boiling n-hexane insoluble fraction (HI), with the boiling n-hexane insoluble fraction being 5 to 30%, and the boiling n-hexane insoluble fraction (HI). Hexane soluble content is 95-70%. Preferably, the boiling n-hexane soluble fraction has an intrinsic viscosity ([η]) (measured at 30°C in toluene) of 1 to 5 and a cis-1,4 structure content.
92% or more, and the intrinsic viscosity ([η]) of the boiling n-hexane insoluble matter (measured at 135°C in tetralin) is 0.5 to
5, the 1,2-structure content is 85% or more, and the melting point is 200 to 220°C. The 1,2-structure portion of the boiling n-hexane insoluble portion mainly has a syndiotactic 1,2-structure. The polybutadiene obtained by the method of the present invention can be blended with known compounding agents conventionally used for natural rubber and high cis-1,4-polybutadiene. Furthermore, the polybutadiene obtained by the method of the present invention can also be used by blending it with natural rubber or other synthetic rubber. Next, examples and comparative examples will be shown. In the description of Examples and Comparative Examples, the boiling n of polybutadiene
-For hexane-insoluble matter, dissolve 2g of reinforced polybutadiene in 200ml of n-hexane at room temperature, then
The insoluble matter was extracted using a Soxhlet extractor for 4 hours, the extracted residue was vacuum-dried, and its weight was precisely weighed. In addition, the boiling n-hexane soluble fraction is the n-hexane soluble fraction obtained as above and the n-hexane soluble fraction extracted by the Soxhlet extractor.
- Determined by removing hexane by evaporation, vacuum drying, and accurately weighing. In addition, the boiling n-hexane soluble content of the reinforced polybutadiene and the cis-1,
The 4-structure content was measured by infrared absorption spectroscopy (IR), the 1,2-structure content of boiling n-hexane-insoluble components was measured by nuclear magnetic resonance spectroscopy (NMR), and the melting point of boiling n-hexane-insoluble components was measured by nuclear magnetic resonance spectroscopy (NMR). (MP) was determined by the peak temperature of the endothermic curve measured by a self-recording differential calorimeter (DSC). In addition, the boiling n-hexane soluble content of the reinforced polybutadiene and the intrinsic viscosity ([η]) of the polybutadiene after cis-1,4 polymerization are the values measured in toluene at 30°C. The intrinsic viscosity ([η]) of the hexane-insoluble portion is the value measured in tetralin at 135°C. Example 1 85 g of dried 1,3-butadiene was dissolved in 860 ml of dehydrated benzene in a separable flask with an inner volume of 2 and equipped with a thermometer, a stirring rod, and a nitrogen gas inlet tube, with the air replaced with nitrogen. Add a benzene solution of 3-butadiene (containing 1.0 mmol of water),
While keeping the liquid temperature at 70â, add 4.6 mmol of cyclooctadiene and 4.0 mmol of diethylaluminum monochloride to this benzene solution of 1,3-butadiene.
After sequentially adding mmol of cobalt octoate and 0.043 mmol of cobalt octoate with stirring, cis-1,4 polymerization of 1,3-butadiene was carried out at 40° C. for 10 minutes while continuing to stir. The polymer had a cis-1,4 structure content of 96% or more and [η] of 2.4.
Immediately after cis-1,4 polymerization, n-butyllithium
After adding 2.0 mmol and 0.13 mmol of carbon disulfide, 1,3-butadiene was 1,2-polymerized at 40° C. for 8 minutes with stirring. A small amount of 2,6-di-tert-butyl-4-methylphenol and 1 methanol containing hydrochloric acid were added to the resulting polymer product mixture to terminate the polymerization reaction. The precipitated polymer was collected and dried under reduced pressure at about 20°C to obtain 50.8 g of polybutadiene. This polybutadiene contains 15.7% boiling n-hexane insoluble matter, 15.7% boiling n-hexane insoluble matter,
2-The structural content is 92.0%, the melting point is 204â, the intrinsic viscosity ([η]) is 4.0, and the cis-1,4-structural content of the boiling n-hexane soluble fraction is 96.2.
%, and the intrinsic viscosity ([η]) (toluene, 30â) is
It was 2.3. Examples 2 to 6 Example 1 except that the polymerization conditions were changed as shown in Table 1.
I did the same thing. The results are shown in Table 2.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
æ¯èŒäŸ ïŒ
ïœâããã«ãªããŠã ãæ·»å ããªãã€ãä»ã¯å®æœ
äŸïŒãšåæ§ã«ããŠãã·ã¹âïŒïŒïŒæ§é å«æç97ïŒ
ã®ã·ã¹âïŒïŒïŒããªãã¿ãžãšã³65ïœãåŸãããã
å®æœäŸ ïŒ
æ¹æè£
眮ãèšçœ®ããå
容ç©20ã®ãªãŒãã¯ã¬ãŒ
ãã«24ééïŒ
ã®ïŒïŒïŒâãã¿ãžãšã³ãå«ããã³ãŒ
ã³æº¶æ¶²ã15å
¥ããæ°Žåæ¿åºŠã1.4ããªã¢ã«ïŒ
ã«èª¿ç¯ããã22âã«ãããŠãžãšãã«ã¢ã«ãããŠã
ã¢ãã¯ããªã49.5ããªã¢ã«ãïŒïŒïŒâã·ã¯ããªã¯
ã¿ãžãšã³13ïœãå ã40âã«ææž©ããã³ãã«ããªã¯
ããšãŒã0.17ããªã¢ã«ãå ããŠå·åŽããªãã40â
ã«ãããŠ30åéåããã
ãã®åŸããã®æº¶æ¶²äžã«ïœâããã«ãªããŠã 25ã
ãªã¢ã«ãã³ãã«ããªã¯ããšãŒã0.15ããªã¢ã«ãäº
ç¡«åççŽ 1.95ããªã¢ã«ã次ã
ã«å ããŠ40âã§30å
åå¿ããã
ããªããŒçææ··åç©äžã«ãæ¿å¡©é
ž30ããªãªãã
ã«ã60ïœã®ïŒïŒïŒâãžç¬¬ïŒâããã«âïŒâã¡ãã«
ããšããŒã«ãå«ãã¡ã¿ããŒã«ïŒãå ãéåãå
æ¢ããããã®åŸãããªããŒæº¶æ¶²ã15ã®ã¡ã¿ããŒ
ã«ãå
¥ãã貯槜ã«æ¹æããªããå ããããªããŒã
æåºæ²æŸ±ããããããªããŒã¯45â以äžã§äžå€ç空
也ç¥ãããããªããŒåéã¯1.25Kgã§ãã€ãã
ãã®ããªããŒã¯æ²žéš°ïœâãããµã³äžæº¶åã12.7
ïŒ
å«ã¿ã沞隰ïœâãããµã³äžæº¶åã®ïŒïŒïŒâæ§é
å«æçã93.2ïŒ
ã§ãããèç¹ã205âã§ãããåº
æç²åºŠã4.2ã§ãã沞隰ïœâãããµã³å¯æº¶åã®ã·
ã¹âïŒïŒïŒâæ§é å«æçã98.3ïŒ
ã§ãããåºæç²
床ã2.1ã§ãã€ãã[Table] Comparative Example 1 The cis-1,4 structure content was 97% in the same manner as in Example 1 except that n-butyllithium was not added.
65 g of cis-1,4 polybutadiene was obtained. Example 7 A benzene solution containing 24% by weight of 1,3-butadiene was put into an autoclave with an internal volume of 20 and equipped with a stirring device, and the water concentration was adjusted to 1.4 mmol/1.
It was adjusted to At 22°C, 49.5 mmol of diethylaluminium monochloride and 13 g of 1,5-cyclooctadiene were added, and the temperature was raised to 40°C. 0.17 mmol of cobalt octoate was added, and the temperature was raised to 40°C while cooling.
Polymerization was carried out for 30 minutes. Thereafter, 25 mmol of n-butyllithium, 0.15 mmol of cobalt octoate, and 1.95 mmol of carbon disulfide were successively added to this solution, and the mixture was reacted at 40° C. for 30 minutes. Polymerization was terminated by adding 30 ml of concentrated hydrochloric acid and 3 methanol containing 60 g of 2,6-di-tert-butyl-4-methylphenol to the polymer production mixture. Thereafter, the polymer solution was added to a storage tank containing 15 methanol with stirring to precipitate the polymer. The polymer was dried under vacuum overnight below 45°C. Polymer yield was 1.25Kg. This polymer has a boiling n-hexane insoluble content of 12.7
%, the 1,2-structure content of the boiling n-hexane insoluble fraction is 93.2%, the melting point is 205°C, the intrinsic viscosity is 4.2, and the boiling n-hexane soluble fraction has a cis-1,4- structure content of 93.2%. The structural content was 98.3% and the intrinsic viscosity was 2.1.
第ïŒå³ã¯ãã®çºæã®ããªãã¿ãžãšã³è£œé æ³ã®æµ
ãã瀺ããããŒãã€ãŒãå³ã§ããã
FIG. 1 is a flowchart showing the flow of the polybutadiene production method of the present invention.
Claims (1)
溶æ§ã³ãã«ãååç©ããã³ææ©ã¢ã«ãããŠã ãã©
ã€ããããªãã·ã¹âïŒïŒïŒéå觊åªã®ååšäžã«
ïŒïŒïŒâãã¿ãžãšã³ãéåããŠãã·ã¹âïŒïŒïŒæ§
é å«æçã90ïŒ ä»¥äžã§åºæç²åºŠ[η]ãïŒãïŒïŒãã«
ãšã³äž30âã§æž¬å®ïŒã§ããã·ã¹âïŒïŒïŒããªãã¿
ãžãšã³ãçæãããç¶ããŠãã®éåç³»ã«å¯æº¶æ§ã³
ãã«ãååç©ãææ©ã¢ã«ãããŠã ãã©ã€ããææ©
ãªããŠã ååç©ããã³äºç¡«åççŽ ãããã¯ã€ãœã
ãªã·ã¢ã³é žããšãã«ãããªãïŒïŒïŒâéå觊åªã
ååšãããŠïŒïŒïŒâãã¿ãžãšã³ãéåããŠã沞隰
ïœâãããµã³äžæº¶åãïŒã30ïŒ ã沞隰ïœâãããµ
ã³å¯æº¶åã95ã70ïŒ ã§ããæçµããªãã¿ãžãšã³ã
çæãããããšãç¹åŸŽãšããè£åŒ·ããªãã¿ãžãšã³
ã®è£œé æ³ã ïŒ ïŒïŒïŒâãã¿ãžãšã³ã®éå溶åªæº¶æ¶²äžã«
50ppm以äžã®æ¿åºŠã§æ°ŽåãååšããïŒïŒïŒâéå
觊åªã®äžæåã§ããææ©ãªããŠã ååç©ãåèšæ°Ž
åã«å¯ŸããŠçã¢ã«é以äžååšããç¹èš±è«æ±ã®ç¯å²
第ïŒé èšèŒã®è£œé æ³ã[Scope of Claims] 1. 1,3-Butadiene is polymerized in a polymerization solvent solution of 1,3-butadiene in the presence of a cis-1,4 polymerization catalyst consisting of a soluble cobalt compound and an organoaluminium halide to produce cis-1,3-butadiene. A cis-1,4 polybutadiene with a -1,4 structure content of 90% or more and an intrinsic viscosity [η] of 1 to 4 (measured at 30°C in toluene) is produced, and then a soluble cobalt compound is added to this polymerization system. , 1,3-butadiene is polymerized in the presence of a 1,2-polymerization catalyst consisting of an organoaluminum halide, an organolithium compound, and carbon disulfide or phenyl isothiocyanate, so that the content insoluble in boiling n-hexane is 5 to 30%, A method for producing reinforced polybutadiene, characterized in that a final polybutadiene is produced with a boiling n-hexane soluble content of 95 to 70%. 2 In a polymerization solvent solution of 1,3-butadiene
2. The production method according to claim 1, wherein water is present at a concentration of 50 ppm or less, and the organolithium compound, which is a component of the 1,2-polymerization catalyst, is present in an equimolar amount or more relative to the water.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1092382A JPS58129014A (en) | 1982-01-28 | 1982-01-28 | Preparation of reinforced polybutadiene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1092382A JPS58129014A (en) | 1982-01-28 | 1982-01-28 | Preparation of reinforced polybutadiene |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS58129014A JPS58129014A (en) | 1983-08-01 |
JPS6320443B2 true JPS6320443B2 (en) | 1988-04-27 |
Family
ID=11763754
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1092382A Granted JPS58129014A (en) | 1982-01-28 | 1982-01-28 | Preparation of reinforced polybutadiene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS58129014A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6173707A (en) * | 1984-09-19 | 1986-04-15 | Ube Ind Ltd | Polybutadiene rubber |
CN117106116B (en) * | 2023-10-25 | 2024-02-13 | äŒ åæºèè¡ä»œæéå ¬åž | MFU-4l catalyst containing Nd and Al elements, preparation method thereof and application thereof in preparing polybutadiene |
-
1982
- 1982-01-28 JP JP1092382A patent/JPS58129014A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS58129014A (en) | 1983-08-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0034235B1 (en) | Process for producing polybutadiene rubber with enhanced mechanical strength | |
EP1134233B1 (en) | Novel monomeric neodymium carboxylate and its use in polymerization of conjugated diene | |
JPH07188341A (en) | Production of cis-1,4-polybutadiene with reduced gel formation | |
JPH0356566B2 (en) | ||
US3935180A (en) | Polybutadiene and process for producing same | |
JPH1077310A (en) | Cobalt-containing catalyst system | |
JPS5964609A (en) | Production of reinforced polybutadiene | |
JPS6320443B2 (en) | ||
JPS58109513A (en) | Production of reinforced polybutadiene rubber | |
JPS58109512A (en) | Production of reinforced polybutadiene rubber | |
JPH0356567B2 (en) | ||
WO2002102861A2 (en) | Process for the (co)polymerization of conjugated dienes | |
US4504639A (en) | Process for polymerizing 1,3-butadiene | |
JPH0238081B2 (en) | HOKYOHORIBUTA JENGOMUNOSEIZOHO | |
JPS6128684B2 (en) | ||
JPH0237927B2 (en) | HOKYOHORIBUTA JENNOSEIZOHO | |
JPS6324604B2 (en) | ||
JPS608307A (en) | Production of reinforced polybutadiene | |
JPS5915413A (en) | Short-stopping of polymerization | |
JPS6216201B2 (en) | ||
JPH0834822A (en) | Production of reinforced polybutadiene | |
JPH06298867A (en) | Production of butadiene polymer | |
JPS6138722B2 (en) | ||
JPS6138723B2 (en) | ||
JPH10237123A (en) | Production of polybutadiene |