CN105348415B - 一种水杨醛胺基稀土金属催化剂、制备方法及应用 - Google Patents
一种水杨醛胺基稀土金属催化剂、制备方法及应用 Download PDFInfo
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- CN105348415B CN105348415B CN201510690192.8A CN201510690192A CN105348415B CN 105348415 B CN105348415 B CN 105348415B CN 201510690192 A CN201510690192 A CN 201510690192A CN 105348415 B CN105348415 B CN 105348415B
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- Prior art keywords
- aluminium
- salicylide
- amido
- methyl
- earth metal
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- -1 amido rare-earth metal Chemical class 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 97
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000001336 alkenes Chemical class 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 32
- 150000001412 amines Chemical class 0.000 claims abstract description 26
- 150000001638 boron Chemical class 0.000 claims abstract description 19
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 18
- 150000001925 cycloalkenes Chemical class 0.000 claims abstract description 17
- 239000000376 reactant Substances 0.000 claims abstract description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 11
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000001953 recrystallisation Methods 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 70
- 239000004411 aluminium Substances 0.000 claims description 67
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 39
- 125000003368 amide group Chemical group 0.000 claims description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000005660 chlorination reaction Methods 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229910052765 Lutetium Inorganic materials 0.000 claims description 15
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229910052706 scandium Inorganic materials 0.000 claims description 13
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 12
- 229910052727 yttrium Inorganic materials 0.000 claims description 12
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229960002685 biotin Drugs 0.000 claims description 10
- 235000020958 biotin Nutrition 0.000 claims description 10
- 239000011616 biotin Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 9
- 239000003208 petroleum Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- INYFUJWBAYHXTG-UHFFFAOYSA-N (2-ethenylphenyl)methanamine Chemical compound NCC1=CC=CC=C1C=C INYFUJWBAYHXTG-UHFFFAOYSA-N 0.000 claims description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001896 cresols Chemical class 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 5
- HEVGGTGPGPKZHF-UHFFFAOYSA-N 1-(1,2-dimethyl-3-methylidenecyclopentyl)-4-methylbenzene Chemical compound CC1C(=C)CCC1(C)C1=CC=C(C)C=C1 HEVGGTGPGPKZHF-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002971 oxazolyl group Chemical group 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 2
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 claims description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 2
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 claims description 2
- AQZRARFZZMGLHL-UHFFFAOYSA-N 2-(trifluoromethyl)oxirane Chemical compound FC(F)(F)C1CO1 AQZRARFZZMGLHL-UHFFFAOYSA-N 0.000 claims description 2
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 claims description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 claims description 2
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 claims description 2
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 claims description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 240000000203 Salix gracilistyla Species 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 229910000091 aluminium hydride Inorganic materials 0.000 claims description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 claims description 2
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 claims description 2
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
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- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 claims description 2
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- 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
- C08F4/52—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 selected from boron, aluminium, gallium, indium, thallium or rare earths
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- C08F138/00—Homopolymers of compounds having one or more carbon-to-carbon triple bonds
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- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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Abstract
本发明公开了一种水杨醛胺基稀土金属催化剂、制备方法及应用,属于催化剂技术领域。所述催化剂结构式如式Ⅰ所示;所述催化剂是先将反应物a、反应物b、低聚甲醛和甲醇加入到反应器1中反应,降温,去除甲醇,纯化,得到水杨醛胺配体;再将水杨醛胺配体溶于甲苯中后加入金属源,低温下搅拌反应6~12h后升至室温,过滤,浓缩,重结晶,得到所述催化剂;所述催化剂单独使用,或与烷基铝试剂和有机硼盐组成的催化体系,可用于直链烯烃、支链烯烃、环烯烃、炔烃和极性单体的均聚反应,或其中两种或三种的共聚反应,或直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种或两种与CO2的共聚反应。
Description
技术领域
本发明涉及一种水杨醛胺基稀土金属催化剂、制备方法及应用,属于催化剂技术领域。
背景技术
非茂配体与稀土金属配位合成稀土金属催化剂,一直以来都是非茂配体研究的主要方向。由于稀土金属中的镧系元素含有4f轨道,多数稀土金属在其化合物中一般是以+3价氧化态存在的。由于稀土金属离子半径大、配位数高,对底物的配位和活化极其有利,故稀土金属有机化合物有自己独特的性质。原子中的4f轨道有其自身的一些特性,主要表现在受到屏蔽作用后不再参与化学键的形成,所以d区过渡金属元素的许多规则例如18电子规则等也不能用于稀土金属有机化学。像氧化加成与还原消除这类在d区过渡金属有机配合物化学中典型的反应,在稀土金属有机配合物化学中却很少发生。虽然稀土金属是副族元素,但是稀土元素能与氮元素或者碳元素等形成σ键,这些化学键往往表现出较强的离子性和高的反应活性。
稀土金属离子是硬Lewis酸,表现出Lewis酸的一些特性,易于与含N、O 原子的配体配位,表现出很强的亲氧性,而与烯烃、有机磷及一氧化碳等的软配位能力比较弱。
上世纪50年代到90年代中期,茂稀土金属有机配体占据了稀土催化剂研究领域的主导地位,其代表是环戊二烯基和它的一系列衍生物。然而,茂稀土配体自身也存在许多缺陷,比如说制备步骤相对繁琐难以得到,生成的化合物结构相对较少,稳定性难以调控,反应活性与催化性能不够理想。为了解决这些挑战,稀土金属有机配体扩展到了茂配体体系之外的非茂体系。在非茂体系中,一系列杂原子基团被巧妙地运用,配体中的胺基、胍基、脒基、烷氧基、吡咯、吡唑和碳硼烷等的运用,可合成极具潜力的一系列配体。
目前报道的水杨醛胺配体已经与某些过渡金属形成有机金属化合物,尽管这些以水杨醛胺基为支撑的金属有机化合物对某些烯烃聚合反应表现出一定的活性和选择性,但是依然存在活性低和选择性差的问题。
发明内容
有鉴于此,本发明的目的之一在于提供一种水杨醛胺基稀土金属催化剂,所述催化剂具有较高的催化活性和选择性;本发明的目的之二在于提供一种水杨醛胺基稀土金属催化剂的制备方法,所述方法经济效率高、环保性好,适合工业化生产;本发明的目的之三在于提供一种水杨醛胺基稀土金属催化剂的应用,所述催化剂与烷基铝试剂和有机硼盐组成的催化体系,可进行直链烯烃、支链烯烃、环烯烃、炔烃、极性单体的均聚及共聚反应或支链烯烃、环烯烃、炔烃、极性单体与CO2的共聚反应,得到一系列具有特定结构的聚合材料。
本发明的目的由以下技术方案实现:
一种水杨醛胺基稀土金属催化剂,所述水杨醛胺基稀土金属催化剂结构式如下:
其中,所述Ln是稀土金属,优选为钪(Sc)、钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nb)、钷(Pm)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)或镥(Lu);
所述R10是与Ln相连的引发基团,优选为甲基、乙基、异丙基、三甲基硅甲基、苄基,甲氧基、乙氧基、苯氧基、苄氧基、二(三甲基硅)氨基、三甲基硅氨基、烯丙基、四氢硼烷、八甲基二铝、SY、PY2、氟、氯、溴和碘中的一种;所述SY中Y为甲基、乙基、异丙基、三甲基硅甲基和苄基中的一种;所述PY2中Y为甲基、乙基、异丙基、三甲基硅甲基和苄基中的一种或两种;
所述R10′是转移到水杨醛胺配体中烯烃端碳的基团,其中R10′=R10;
所述R1、R2、R3、R4、R6、R7、R8和R9是水杨醛胺配体骨架上的取代基; R1、R2、R3、R4、R6、R7、R8和R9分别独立优选为氢原子、甲基、乙基、烷氧基、氨基、金刚烷基、腈基或生物素;
所述R5是水杨醛胺骨架中N原子上的取代基团,优选为氢原子、烷基、烷氧基、苯基、苄基、胺基、吡啶基、恶唑基或生物素;
所述L1为三苯基磷、乙醚、乙二醇二甲醚、四氢呋喃、吡啶、苯或苯的衍生物;
所述n取1或2;
一种水杨醛胺基稀土金属催化剂的制备方法,所述方法步骤如下:
(1)制备水杨醛胺配体;
将反应物a、反应物b、低聚甲醛和甲醇加入到反应器1中,于55~75℃下搅拌反应36~72h;降温至18~30℃,去除甲醇,纯化,得到水杨醛胺配体;
所述纯化优选采用柱层析色谱法,洗脱剂为乙酸乙酯和石油醚的混合溶液,其中乙酸乙酯与石油醚的体积比为1:50;
其中,所述反应物a、反应物b、低聚甲醛与甲醇的摩尔比为1:1:1.5:35,所述1:1:1.5:3保留小数点后1位得到;
所述反应物a为甲酚或甲酚衍生物,反应物b为2-乙烯基苄胺或2-乙烯基苄胺衍生物;
所述甲酚衍生物优选其中R1、R2、R3和R4为氢原子、甲基、乙基、烷氧基、氨基、金刚烷基、腈基或生物素;
所述2-乙烯基苄胺衍生物优选其中R5为氢原子、烷基、烷氧基、苯基、苄基、胺基、吡啶基、恶唑基或生物素;R6、R7、R8和R9为氢原子、甲基、乙基、烷氧基、氨基、金刚烷基、腈基或生物素;
(2)制备水杨醛胺基稀土金属催化剂
将水杨醛胺配体溶于甲苯中,得到溶液a;将反应器2置于手套箱中,将金属源的甲苯溶液添加到反应器2中,在搅拌下,逐滴加入溶液a,将反应器2密封转移到-25~-35℃下搅拌反应6~12h;升温至18~30℃,将反应器2放回手套箱中,过滤反应器2中的反应液,取滤液进行浓缩和重结晶处理,得到本发明所述水杨醛胺基稀土催化剂;
其中,所述甲苯中的水含量小于5ppm;所述低聚甲醛的相对分子量为90.08;
所述金属源优选二四氢呋喃-三(三甲基硅甲基)稀土金属化合物 (Ln(CH2SiMe3)3(thf)2);
水杨醛胺配体与金属源的摩尔比为1:1;
一种水杨醛胺基稀土金属催化剂的应用,所述水杨醛胺基稀土金属催化剂,水杨醛胺基稀土金属催化剂与烷基铝试剂和有机硼盐组成的催化体系,可用于直链烯烃、支链烯烃、环烯烃、炔烃和极性单体的均聚反应,或其中两种或三种的共聚反应,或直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种或两种与CO2的共聚反应;
其中,所述催化体系中有机硼盐、烷基铝试剂与水杨醛胺基稀土金属催化剂的摩尔比为1~100:2~100:1;烷基铝试剂优选分子式为AlR3的烷基铝、分子式为HAlR2的烷基氢化铝、分子式为AlR2Cl的烷基氯化铝或铝氧烷;
所述聚合反应的步骤如下:
方法一:
将反应器3置于手套箱中,并向反应器3中依次加入水杨醛胺基稀土金属催化剂,良溶剂和单体,于-30~90℃搅拌下反应0.3~72h;取出反应器3,并加入链终止剂,使反应中止;将反应液用不良溶剂进行沉降,析出固体物质;将所述固体物质于30~70℃下真空干燥至恒重,得到目标产物;
所述单体与水杨醛胺基稀土催化剂的摩尔比为200~5000:1;单体与良溶剂形成的溶液浓度为0.2~0.5g/mL;
方法二:
将反应器4置于手套箱中,并向反应器4中依次加入水杨醛胺基稀土金属催化剂,良溶剂,烷基铝试剂,单体和有机硼盐,于-30~90℃搅拌下反应0.3~ 72h;取出反应器4,并加入链终止剂,使反应中止;将反应液用不良溶剂进行沉降,析出固体物质;将所述固体物质于30~70℃下真空干燥至恒重,得到目标产物;
所述单体,烷基铝,有机硼盐与水杨醛胺基稀土催化剂的摩尔比为200~ 5000:2~100:1~100:1;单体与良溶剂形成的溶液浓度为1~100×10-5g/mL;
其中,所述不良溶剂优选甲醇、乙醇、正己烷和石油醚溶剂中的一种;
当均聚时:所述单体为直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种;
当共聚时:所述单体为直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的两种或三种,或直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种或两种和CO2;
其中,所述链状烯烃优选为乙烯、丙烯、1-丁烯、2-丁烯、1-戊烯、2-戊烯、 4-甲基-1-戊烯、1-己烯、2-己烯、3-己烯、1-庚烯、2-庚烯、1-辛烯、2-辛烯、1- 癸烯、2-癸烯、1-十二碳烯、2-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯,苯乙烯、1-甲基苯乙烯、2-甲基苯乙烯、3-氯甲基苯乙烯、1,3- 丁二烯、异戊二烯、1,5-戊二烯、1,6-己二烯、二乙烯基苯、月桂烯和罗勒烯中的一种;
所述环状烯烃优选为1,3-环戊二烯、1,3-环己二烯、降冰片烯、降冰片二烯、亚乙基降冰片烯、乙烯基降冰片烯、苯基降冰片烯、降冰片烯碳酸甲酯、降冰片烯碳酸乙酯和二环戊二烯中的一种;
所述炔烃优选为乙炔、对苯乙二炔、二乙炔基芳烃或苯基乙炔;
所述极性单体优选为环氧乙烷、环氧丙烷、三氟环氧丙烷、环氧氯丙烷、环氧溴丙烷、1,2-环氧丁烷、2,3-环氧丁烷、甲基丙烯酸甲酯、甲基丙烯酸乙酯、乙基丙烯酸甲酯、乙基丙烯酸乙酯、甲基缩水甘油醚、2-乙基亚己基缩水甘油醚、烯丙基缩水甘油醚、丁基缩水甘油醚、ε-己内酯,β-丁内酯,δ-戊内酯,丙交酯,乙交酯和3-甲基-乙交酯中的一种;
所述AlR3优选三甲基铝、三乙基铝、三正丙基铝、三正丁基铝、三异丙基铝、三异丁基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苄基铝、乙基二对甲苯基铝或二乙基苄基铝;
所述烷基氢化铝优选氢化二甲基铝、氢化二乙基铝、氢化二正丙基铝、氢化二正丁基铝、氢化二异丙基铝、氢化二异丁基铝、氢化二戊基铝、氢化二己基铝、氢化二环己基铝、氢化二辛基铝、氢化二苯基铝、氢化二对甲苯基铝、氢化二苄基铝、氢化乙基苄基铝或氢化乙基对甲苯基铝;
所述烷基氯化铝优选氯化二甲基铝、氯化二乙基铝、氯化二正丙基铝、氯化二正丁基铝、氯化二异丙基铝、氯化二异丁基铝、氯化二戊基铝、氯化二己基铝、氯化二环己基铝、氯化二辛基铝、氯化二苯基铝、氯化二对甲苯基铝、氯化二苄基铝、氯化乙基苄基铝或氯化乙基对甲苯基铝;
所述铝氧烷优选甲基铝氧烷、乙基铝氧烷、正丙基铝氧烷或正丁基铝氧烷;
所述的有机硼盐优选三苯基(甲基)-四(五氟苯)硼盐([Ph3C][B(C6F5)4])、苯基-二甲基氨基-四(五氟苯)硼盐([PhMe2NH][B(C6F5)4])、苯基-二甲基氨基- 四苯基硼盐([PhMe2NH][BPh4])、氯化硼(BCl3)或三(五氟苯)硼盐(B(C6F5)3);
所述链终止剂为质量浓度均为5%的2,6-二叔丁基对甲酚的乙醇溶液、2,3,4- 三甲基苯酚的乙醇溶液、间二苯酚的乙醇溶液、2,6-二乙基苯酚的乙醇溶液或对叔丁基苯酚的乙醇溶液。
有益效果
(1)本发明所述的水杨醛胺基稀土金属催化剂含有一个sp3杂化碳原子与稀土金属原子相连而形成的六元环结构,使得催化剂在催化活性、聚合产物选择性和聚合产物分子量方面有了明显提高;
(2)本发明所述制备方法,经济效率高、环保性好,且所用配体的原料廉价易得,合成方法简单,适合工业化生产。
(3)本发明所述水杨醛胺基稀土金属催化剂,水杨醛胺基稀土金属催化剂与烷基铝试剂和有机硼盐组成的催化体系,可进行链状烯烃、环烯烃、炔烃、极性单体的均聚及共聚反应,或链状烯烃、环烯烃、炔烃、极性单体与CO2的共聚反应,得到一系列具有特定结构的聚合材料。
(4)本发明所述水杨醛胺基稀土金属催化剂属于非茂稀土金属催化剂,同时在一些单体的聚合效果上超越了茂稀土金属催化剂,特别是单水杨醛胺基钇单烷基催化剂在2-乙烯基吡啶聚合反应中表现出高的聚合活性(最高可达 1.3×105g·mol-1·h-1),全同立构率达到95%,数均分子量为0.5~100万范围内,具有双峰模型的分子量分布Mw/Mn=1.48~6.07。
附图说明
图1为实施例1中制备的单水杨醛胺基钇催化剂的X-射线单晶衍射表征的晶体结构图;
图2为实施例2中制备的单水杨醛胺基镥催化剂的X-射线单晶衍射表征的晶体结构图;
图3为实施例3中制备的单水杨醛胺基钪催化剂的X-射线单晶衍射表征的晶体结构图。
具体实施方式
下面结合附图和具体实施例来详述本发明,但不限于此。
以下实施例中提到的主要试剂信息见表1;主要仪器与设备信息见表2。
表1
表2
以下实施例中涉及到的物理量由以下方法得到:
(1)产率:实际产量/理论产量。
(2)聚合物选择性:通过聚合物的1H和13C核磁谱图得到。
(3)Mn:聚合物的分子量,通过渗透凝胶色谱(GPC)测试得到。
(4)Mw/Mn:聚合物的分子量分布,通过GPC测试得到。
(5)聚合活性:(得到聚合物的质量/催化剂的摩尔量)/聚合时间,单位为 Kg/mol/h。
以下实施例中所述的重蒸甲苯中的水含量小于5ppm;所述链终止剂为含 2,6-二叔丁基-4-甲基苯酚的乙醇,以乙醇的质量为100%计,其中,2,6-二叔丁基 -4-甲基苯酚占5%;所述低聚甲醛的相对分子量为90.08。
实施例1
一种单水杨醛胺基钇催化剂的制备方法,所述方法步骤如下:
(1)制备水杨醛胺配体
将5.61mmol 2-(1-金刚烷基)-4-甲酚,5.55mmol N-甲基-1-(2-乙烯基)甲胺和8.59mmol低聚甲醛加入到25mL的茄瓶中,并加入8mL甲醇作为溶剂,将茄瓶放入65℃的油浴中,在搅拌下,反应48h;将茄瓶冷却恢复到25℃,在真空下将甲醇抽干,以体积比为1:50的乙酸乙酯和石油醚的混合溶液作为洗脱剂,采用柱层析色谱法进行纯化,得到无色液体,真空抽干溶剂得到白色固体,即为水杨醛胺配体;所述水杨醛胺配体的结构式如式Ⅰ所示;
(2)制备单水杨醛胺基钇催化剂
将2.5mmol水杨醛胺配体溶解于20mL重蒸甲苯中,得到溶液a;将三口烧瓶置于手套箱中,将溶有2.5mmol Y(CH2SiMe3)3(thf)2的重蒸甲苯溶液添加到三口烧瓶中,在搅拌下,逐滴加入溶液a,在氮气保护下,将三口烧瓶密封转移到转移到-30℃条件下,搅拌反应10h;升温至25℃,将反应器2放回手套箱中,过滤反应器2中的反应液,取滤液进行浓缩和重结晶处理,得到1.42g淡黄色粉末;所述淡黄色粉末的X-射线单晶衍射表征的晶体结构图如图1所示,结构式如式Ⅱ所示,结合图1和式Ⅱ可知,所述淡黄色粉末即为所述单水杨醛胺基钇,产率为86%。
实施例2
一种单水杨醛胺基镥催化剂的制备方法,所述方法步骤如下:
(1)制备水杨醛胺配体
将5.61mmol 2-(1-金刚烷基)-4-甲酚,5.55mmol N-甲基-1-(2-乙烯基)甲胺和8.59mmol低聚甲醛加入到25mL的茄瓶中,并加入8mL甲醇作为溶剂,将茄瓶放入55℃的油浴中,在搅拌下,反应72h;将茄瓶冷却恢复到18℃,在真空下将甲醇抽干,以体积比为1:50的乙酸乙酯和石油醚的混合溶液作为洗脱剂,采用柱层析色谱法进行纯化,得到无色液体,真空抽干溶剂得到白色固体,即为水杨醛胺配体;所述水杨醛胺配体的结构式如式Ⅰ所示;
(2)制备单水杨醛胺基镥催化剂
将2.5mmol水杨醛胺配体溶解于20mL重蒸甲苯中,得到溶液a;将三口烧瓶置于手套箱中,将溶有2.5mmol Lu(CH2SiMe3)3(thf)2的重蒸甲苯溶液添加到三口烧瓶中,在搅拌下,逐滴加入溶液a,在氮气保护下,将三口烧瓶密封转移到 -25℃条件下,搅拌反应6h;升温至18℃,将三口烧瓶放回手套箱中,三口烧瓶中的反应液,取滤液进行浓缩和重结晶处理,得到1.53g淡黄色粉末;所述淡黄色粉末的X-射线单晶衍射表征的晶体结构图如图2所示,结构式如式Ⅲ所示,结合图2和式Ⅲ可知,所述淡黄色粉末即为所述单水杨醛胺基镥,产率为82%。
实施例3
(1)制备水杨醛胺配体
将5.61mmol 2,4-二(三叔丁基)苯酚,5.55mmol N-甲基-1-(2-乙烯基)甲胺和8.59mmol低聚甲醛加入到25mL的茄瓶中,并加入8mL甲醇作为溶剂,将茄瓶放入75℃的油浴中,在搅拌下,反应36h;将茄瓶冷却恢复到30℃,在真空下将甲醇抽干,以体积比为1:50的乙酸乙酯和石油醚的混合溶液作为洗脱剂,采用柱层析色谱法进行纯化,得到无色液体,真空抽干溶剂得到白色固体,即为水杨醛胺配体;所述水杨醛胺配体的结构式如式Ⅳ所示;
(2)制备单水杨醛胺基钪催化剂
将2.74mmol水杨醛胺配体溶解于20mL重蒸甲苯中,得到溶液a;将三口烧瓶置于手套箱中,将溶有2.74mmol Sc(CH2SiMe3)3(thf)2的重蒸甲苯溶液添加到三口烧瓶中,在搅拌下,逐滴加入溶液a,在氮气保护下,将三口烧瓶密封转移到转移到-35℃条件下,搅拌反应12h;升温至30℃,将反应器2放回手套箱中,过滤反应器2中的反应液,取滤液进行浓缩和重结晶处理,得到1.38g淡黄色粉末;所述淡黄色粉末的X-射线单晶衍射表征的晶体结构图如图3所示,结构式如式Ⅴ所示,结合图3和式Ⅴ可知,所述淡黄色粉末即为所述单水杨醛胺基钇,产率为86%。
以下实施例4~实施例6为实施例1制备的单水杨醛胺基钇催化剂的应用。
实施例4
将茄瓶置于手套箱中,并向茄瓶中依次加入25μmol单水杨醛胺基钇催化剂,2mL甲苯,50μmol AlMe3,5mmol异戊二烯及25μmol[Ph3C][B(C6F5)4],于-30℃下搅拌反应24h后将茄瓶取出,加入30mL链终止剂,使反应中止;将反应液用乙醇进行沉降,析出白色固体物质,将所述固体物质在30℃下真空干燥,除去甲苯至恒重,得到聚异戊二烯,净重0.34g,转化率100%,聚合活性为0.57kg·mol-1·h-1。GPC分析聚异戊二烯的数均分子量Mn=13×103,分子量分布Mw/Mn=5.24。顺-1,4-聚合选择性100%。
实施例5
将茄瓶置于手套箱中,并向茄瓶中依次加入25μmol单水杨醛胺基钇催化剂,5mL甲苯及5mmol 2-乙烯基吡啶,于30℃下搅拌反应0.3h后将茄瓶取出,加入1mL链终止剂,使反应中止;将反应液用大量正己烷进行沉降,析出白色固体物质,将所述固体物质在70℃下真空干燥,得到聚2-乙烯基吡啶,净重0.53 g,转化率100%,聚合活性为0.013kg·mol-1·h-1。GPC分析聚异戊二烯的数均分子量Mn=13×103,分子量分布Mw/Mn=5.24。全同立构选择性为95%。
实施例6
将茄瓶置于手套箱中,并向茄瓶中依次加入25μmol单水杨醛胺基钇催化剂,5mL甲苯,50μmol AliBu3,5mmol苯乙炔及25μmol[PhNHMe2][B(C6F5)4],反应时间0.3h,反应温度50℃,其余操作同实施例4,得到聚苯乙炔,净重0.51 g,转化率100%。GPC分析聚苯乙炔的数均分子量Mn=10×103,分子量分布 Mw/Mn=2.13。
以下实施例7~实施例14为实施例2制备的单水杨醛胺基镥催化剂的应用。
实施例7
将反应器置于手套箱中,向茄瓶中依次加入25μmol单水杨醛胺基镥催化剂,20mL甲苯,50μmol AliBu3,50mmol D,L-丙交酯及25μmol [PhNHMe2][B(C6F5)4],反应时间2.5h,反应温度25℃,其余操作同实施例4,得到聚D,L-丙交酯,净重6.3g,转化率87%。GPC分析聚D,L-丙交酯的数均分子量Mn=9×104,分子量分布Mw/Mn=2.55。
实施例8
将反应器置于手套箱中,向茄瓶中依次加入25μmol单水杨醛胺基镥催化剂,10mL甲苯,1.2mmol AlMe3,5mmolε-己内酯及1.2mmol[Ph3C][B(C6F5)4],反应时间2.5h,反应温度25℃,其余操作同实施例4,得到聚ε-己内酯,净重 0.43g,转化率75%。GPC分析聚ε-己内酯的数均分子量Mn=6×104,分子量分布 Mw/Mn=2.58。
实施例9
将反应器置于手套箱中,向茄瓶中依次加入25μmol单水杨醛胺基镥催化剂,35mL甲苯,50μmol AlMe3,125mmol环氧丙烷及25μmol[Ph3C][B(C6F5)4],反应时间5h,反应温度50℃,其余操作同实施例4,得到聚环氧丙烷,净重6.5 g,转化率90%。GPC分析聚环氧丙烷的数均分子量Mn=13×104,分子量分布 Mw/Mn=2.62。
实施例10
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基镥催化剂,25mL甲苯,42μmol AliBu3,5mmol异戊二烯,2.5mmol降冰片烯及21 μmol[Ph3C][B(C6F5)4],反应时间2h,反应温度25℃,加入30mL含5%2,6-二叔丁基-4-甲基苯酚的乙醇,使反应中止;将反应液用乙醇进行沉降,析出固体物质,将所述固体物质在30℃下真空干燥,除去甲苯至恒重,得到异戊二烯与降冰片烯的共聚物,GPC分析共聚物的数均分子量Mn=12×103,分子量分布 Mw/Mn=2.91。共聚物中异戊二烯与降冰片烯比例=91:9,聚异戊二烯部分顺-1,4- 聚合选择性88%。
实施例11
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基镥催化剂,25mL甲苯,42μmol AliBu3,5mmol异戊二烯,5mmol苯乙烯及21 μmol[Ph3C][B(C6F5)4],反应时间72h,反应温度-30℃,其余操作同实施例10,得到异戊二烯与苯乙烯的共聚物,转化率93%。GPC分析共聚物的数均分子量 Mn=4×103,分子量分布Mw/Mn=2.29。
实施例12
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基镥催化剂,25mL甲苯,42μmol AliBu3,5mmol异戊二烯,5mmol 1,3-环己二烯及21 μmol[Ph3C][B(C6F5)4],反应时间72h,反应温度-30℃,其余操作同实施例10,得到异戊二烯与1,3-环己二烯的共聚物,转化率90%。GPC分析共聚物的数均分子量Mn=12×103,分子量分布Mw/Mn=2.45。
实施例13
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基镥催化剂,25mL甲苯,42μmol AliBu3,15mmol降冰片烯,5mmol苯乙烯,及21 μmol[Ph3C][B(C6F5)4],反应时间0.3h,反应温度90℃,其余操作同实施例10,得到降冰片烯与苯乙烯的共聚物,转化率100%。GPC分析共聚物的数均分子量 Mn=4×104,分子量分布Mw/Mn=2.20。
实施例14
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基镥催化剂,25mL甲苯,42μmol AliBu3,105mmol降冰片烯,105mmol 1,3-环己二烯,及21μmol[Ph3C][B(C6F5)4],反应时间3h,反应温度25℃,其余操作同实施例 10,得到降冰片烯与1,3-环己二烯的共聚物,转化率97%。GPC分析共聚物的数均分子量Mn=3×104,分子量分布Mw/Mn=2.61。
以下实施例15~实施例22为实施例3制备的单水杨醛胺基钪催化剂的应用。
实施例15
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,25mL甲苯,42μmol AliBu3,53mmol降冰片烯,53mmol 1,4-丁二烯,及 21μmol[Ph3C][B(C6F5)4],反应时间3h,反应温度25℃,其余操作同实施例10,得到降冰片烯与1,4-丁二烯的共聚物,转化率90%。GPC分析共聚物的数均分子量Mn=4.2×104,分子量分布Mw/Mn=1.69。
实施例16
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,25mL甲苯,42μmol AliBu3,10.5mmol 1,5-己二烯及21μmol[Ph3C][B(C6F5)4],反应时间24h,反应温度25℃,其余操作同实施例4,得到聚1,5-己二烯,转化率88%。GPC分析共聚物的数均分子量Mn=11×104,分子量分布Mw/Mn=1.45,聚合物中环戊烷比率为98%,3,4-顺式环戊烷:3,4-反式环戊烷=7:3。
实施例17
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,25mL甲苯,2.1mmol AliBu3,5mmol降冰片烯,5mmol双环戊二烯,及 2.1mmol[Ph3C][B(C6F5)4],反应时间50h,反应温度25℃,其余操作同实施例 10,得到降冰片烯与双环戊二烯的共聚物,转化率95%。GPC分析共聚物的数均分子量Mn=3.8×104,分子量分布Mw/Mn=3.37。
实施例18
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,25mL甲苯,1.2mmol AliBu3,5mmol异戊二烯,5mmol 1,4-丁二烯,及1.2 mmol[Ph3C][B(C6F5)4],反应时间3h,反应温度90℃,其余操作同实施例10,得到异戊二烯与1,4-丁二烯的共聚物,转化率99%。GPC分析共聚物的数均分子量Mn=4×104,分子量分布Mw/Mn=1.77。
实施例19
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,25mL甲苯,42μmol AliBu3,5mmol异戊二烯,5mmol双环戊二烯,及21 μmol[Ph3C][B(C6F5)4],反应时间3h,反应温度-30℃,其余操作同实施例10,得到异戊二烯与双环戊二烯的共聚物,转化率90%。GPC分析共聚物的数均分子量Mn=15×104,分子量分布Mw/Mn=1.29。
实施例20
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,20mL甲苯,42μmol AliBu3,5mmol环氧乙烷,5mmol环氧丙烷,及21 μmol[Ph3C][B(C6F5)4],反应时间3h,反应温度50℃,其余操作同实施例10,得到环氧乙烷与环氧丙烷的共聚物,转化率99%。GPC分析共聚物的数均分子量Mn=9×104,分子量分布Mw/Mn=1.59。
实施例21
将反应器置于手套箱中,向茄瓶中依次加入21μmol单水杨醛胺基钪催化剂,15mL甲苯,42μmol AliBu3,5mmol D,L-丙交酯,5mmolε-己内酯,及21 μmol[Ph3C][B(C6F5)4],反应时间3h,反应温度25℃,其余操作同实施例10,得到D,L-丙交酯与ε-己内酯的共聚物,转化率98%。GPC分析共聚物的数均分子量Mn=8×104,分子量分布Mw/Mn=1.49。
实施例22
将反应器置于手套箱中,向茄瓶中依次加入0.05mol单水杨醛胺基钪催化剂,1mL甲苯,20mol环氧丙烷,密封反应器,转移出手套箱,向反应器中通入CO2,调节压力至6MPa,然后加热至70℃,反应24小时,然后冷却至30℃,用氯仿溶解,加入甲醇得到白色固体,50℃真空烘干,得到环氧丙烷与CO2的共聚物。转化率23.0%。GPC分析共聚物的数均分子量Mn=41.0×103,分子量分布Mw/Mn=2.0。
本发明包括但不限于以上实施例,凡是在本发明精神的原则之下进行的任何等同替换或局部改进,都将视为在本发明的保护范围之内。
Claims (9)
1.一种水杨醛胺基稀土金属催化剂,其特征在于:所述水杨醛胺基稀土金属催化剂结构式如下:
其中,所述Ln为 钪、钇、镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱或镥;
所述R10为甲基、乙基、异丙基、三甲基硅甲基、苄基,甲氧基、乙氧基、苯氧基、苄氧基、二(三甲基硅)氨基、三甲基硅氨基、烯丙基、SY、PY2、氟、氯、溴和碘中的一种,所述R10′=R10;所述SY中Y为甲基、乙基、异丙基、三甲基硅甲基和苄基中的一种;所述PY2中Y为甲基、乙基、异丙基、三甲基硅甲基和苄基中的一种或两种;
所述R1、R2、R3、R4、R6、R7、R8和R9分别独立为氢原子、甲基、乙基、烷氧基、氨基、金刚烷基、腈基或生物素;
所述R5为氢原子、烷基、烷氧基、苯基、苄基、胺基、吡啶基、恶唑基或生物素;
所述L1为三苯基磷、乙醚、乙二醇二甲醚、四氢呋喃、吡啶、苯或苯的衍生物;
所述n取1或2。
2.一种如权利要求1所述的水杨醛胺基稀土金属催化剂的制备方法,其特征在于:所述方法步骤如下:
(1)制备水杨醛胺配体;
将反应物a、反应物b、低聚甲醛和甲醇加入到反应器1中,于55~75℃下搅拌反应36~72h;降温至18~30℃,去除甲醇,纯化,得到水杨醛胺配体;
其中,所述反应物a、反应物b、低聚甲醛与甲醇的摩尔比为1:1:1.5:35;所述反应物a为甲酚或甲酚衍生物,反应物b为2-乙烯基苄胺或2-乙烯基苄胺衍生物;
(2)制备水杨醛胺基稀土金属催化剂
将水杨醛胺配体溶于甲苯中,得到溶液a;将反应器2置于手套箱中,将金属源的甲苯溶液添加到反应器2中,在搅拌下,逐滴加入溶液a,将反应器2密封转移到-25~-35℃下搅拌反应6~12h;升温至18~30℃,将反应器2放回手套箱中,过滤反应器2中的反应液,取滤液进行浓缩和重结晶处理,得到所述水杨醛胺基稀土催化剂;
其中,所述甲苯中的水含量小于5ppm;所述水杨醛胺配体与金属源的摩尔比为1:1。
3.根据权利要求2所述的一种水杨醛胺基稀土金属催化剂的制备方法,其特征在于:步骤(1)所述纯化采用柱层析色谱法,洗脱剂为乙酸乙酯和石油醚的混合溶液,其中,乙酸乙酯与石油醚的体积比为1:50;所述低聚甲醛的相对分子量为90.08;
步骤(2)所述金属源为二四氢呋喃-三(三甲基硅甲基)稀土金属化合物。
4.根据权利要求2所述的一种水杨醛胺基稀土金属催化剂的制备方法,其特征在于:所述甲酚衍生物为其中R1、R2、R3和R4分别独立为氢原子、甲基、乙基、烷氧基、氨基、金刚烷基、腈基或生物素;
所述2-乙烯基苄胺衍生物为其中R5为氢原子、烷基、烷氧基、苯基、苄基、胺基、吡啶基、唖唑基或生物素;R6、R7、R8和R9分别独立为氢原子、甲基、乙基、烷氧基、氨基、金刚烷基、腈基或生物素。
5.一种如权利要求1所述的水杨醛胺基稀土金属催化剂的应用,其特征在于:所述水杨醛胺基稀土金属催化剂,或水杨醛胺基稀土金属催化剂与烷基铝试剂和有机硼盐组成的催化体系,用于直链烯烃、支链烯烃、环烯烃、炔烃和极性单体的均聚反应,或其中两种或三种的共聚反应,或直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种或两种与CO2的共聚反应;
其中,所述催化体系中有机硼盐、烷基铝试剂与水杨醛胺基稀土金属催化剂的摩尔比为1~100:2~100:1。
6.根据权利要求5所述的一种水杨醛胺基稀土金属催化剂的应用,其特征在于:所述聚合反应的步骤如下:
方法一:
将反应器3置于手套箱中,并向反应器3中依次加入水杨醛胺基稀土金属催化剂,良溶剂和单体,于-30~90℃搅拌下反应0.3~72h;取出反应器3,并加入链终止剂,使反应中止;将反应液用不良溶剂进行沉降,析出固体物质;将所述固体物质于30~70℃下真空干燥至恒重,得到目标产物;
其中,所述单体与水杨醛胺基稀土催化剂的摩尔比为200~5000:1;单体与良溶剂形成的溶液浓度为0.2~0.5g/mL;
或方法二:
将反应器4置于手套箱中,并向反应器4中依次加入水杨醛胺基稀土金属催化剂,良溶剂,烷基铝试剂,单体和有机硼盐,于-30~90℃搅拌下反应0.3~72h;取出反应器4,并加入链终止剂,使反应中止;将反应液用不良溶剂进行沉降,析出固体物质;将所述固体物质于30~70℃下真空干燥至恒重,得到目标产物;
其中,所述单体,烷基铝,有机硼盐与水杨醛胺基稀土催化剂的摩尔比为200~5000:2~100:1~100:1;单体与良溶剂形成的溶液浓度为1~100×10-5g/mL;
当所述聚合反应为均聚时:所述单体为直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种;
当所述聚合反应为共聚时:所述单体为直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的两种或三种,或直链烯烃、支链烯烃、环烯烃、炔烃和极性单体中的一种或两种和CO2。
7.根据权利要求6所述的一种水杨醛胺基稀土金属催化剂的应用,其特征在于:所述不良溶剂为甲醇、乙醇、正己烷和石油醚溶剂中的一种;
所述烷基铝试剂为烷基铝、烷基氢化铝、烷基氯化铝或铝氧烷;
所述的有机硼盐为三苯基(甲基)-四(五氟苯)硼盐、苯基-二甲基氨基-四(五氟苯)硼盐、氯化硼、苯基-二甲基氨基-四苯基硼盐或三(五氟苯)硼盐;
所述链终止剂为质量浓度均为5%的2,6-二叔丁基对甲酚的乙醇溶液、2,3,4- 三甲基苯酚的乙醇溶液、间二苯酚的乙醇溶液、2,6-二乙基苯酚的乙醇溶液或对叔丁基苯酚的乙醇溶液。
8.根据权利要求5或6所述的一种水杨醛胺基稀土金属催化剂的应用,其特征在于:所述直链烯烃为乙烯、丙烯、1-丁烯、2-丁烯、1-戊烯、2-戊烯、4-甲基-1-戊烯、1-己烯、2-己烯、3-己烯、1-庚烯、2-庚烯、1-辛烯、2-辛烯、1-癸烯、2-癸烯、1-十二碳烯、2-十二碳烯、1-十四碳烯、1-十六碳烯、1-十八碳烯、1-二十碳烯、1,3-丁二烯、1,5-戊二烯和1,6-己二烯中的一种;所述支链烯烃为苯乙烯、1-甲基苯乙烯、2-甲基苯乙烯、3-氯甲基苯乙烯、异戊二烯、二乙烯基苯、月桂烯和罗勒烯中的一种;
所述环烯烃为1,3-环戊二烯、1,3-环己二烯、降冰片烯、降冰片二烯、亚乙基降冰片烯、乙烯基降冰片烯、苯基降冰片烯、降冰片烯碳酸甲酯、降冰片烯碳酸乙酯和二环戊二烯中的一种;
所述炔烃为乙炔、对苯乙二炔、二乙炔基芳烃或苯基乙炔;
所述极性单体为环氧乙烷、环氧丙烷、三氟环氧丙烷、环氧氯丙烷、环氧溴丙烷、1,2-环氧丁烷、2,3-环氧丁烷、甲基丙烯酸甲酯、甲基丙烯酸乙酯、乙基丙烯酸甲酯、乙基丙烯酸乙酯、甲基缩水甘油醚、2-乙基亚己基缩水甘油醚、烯丙基缩水甘油醚、丁基缩水甘油醚、ε-己内酯,β-丁内酯,δ-戊内酯,丙交酯,乙交酯和3-甲基-乙交酯中的一种。
9.根据权利要求7所述的一种水杨醛胺基稀土金属催化剂的应用,其特征在于:所述烷基铝为三甲基铝、三乙基铝、三正丙基铝、三正丁基铝、三异丙基铝、三异丁基铝、三己基铝、三环己基铝、三辛基铝、三苯基铝、三对甲苯基铝、三苄基铝、乙基二苄基铝、乙基二对甲苯基铝或二乙基苄基铝;
所述烷基氢化铝为氢化二甲基铝、氢化二乙基铝、氢化二正丙基铝、氢化二正丁基铝、氢化二异丙基铝、氢化二异丁基铝、氢化二戊基铝、氢化二己基铝、氢化二环己基铝、氢化二辛基铝、氢化二苯基铝、氢化二对甲苯基铝、氢化二苄基铝、氢化乙基苄基铝或氢化乙基对甲苯基铝;
所述烷基氯化铝为氯化二甲基铝、氯化二乙基铝、氯化二正丙基铝、氯化二正丁基铝、氯化二异丙基铝、氯化二异丁基铝、氯化二戊基铝、氯化二己基铝、氯化二环己基铝、氯化二辛基铝、氯化二苯基铝、氯化二对甲苯基铝、氯化二苄基铝、氯化乙基苄基铝或氯化乙基对甲苯基铝;
所述铝氧烷为甲基铝氧烷、乙基铝氧烷、正丙基铝氧烷或正丁基铝氧烷。
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