CN112358498B - 一种四芳氧基ivb族双核金属配合物及其制备和应用 - Google Patents
一种四芳氧基ivb族双核金属配合物及其制备和应用 Download PDFInfo
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- CN112358498B CN112358498B CN202011165754.4A CN202011165754A CN112358498B CN 112358498 B CN112358498 B CN 112358498B CN 202011165754 A CN202011165754 A CN 202011165754A CN 112358498 B CN112358498 B CN 112358498B
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- tetraaryloxy
- hydrogen
- metal complex
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 26
- -1 aluminum alkoxide Chemical class 0.000 claims abstract description 64
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004711 α-olefin Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 114
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 62
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 58
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004429 atom Chemical group 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical group C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 7
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 5
- 229910052735 hafnium Chemical group 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 5
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 5
- 239000012312 sodium hydride Substances 0.000 claims description 5
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- TVZXZQOUICFFCL-UHFFFAOYSA-M chloro(ethyl)alumane Chemical group CC[AlH]Cl TVZXZQOUICFFCL-UHFFFAOYSA-M 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000006239 protecting group Chemical group 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 2
- 150000002170 ethers Chemical class 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 17
- 239000005977 Ethylene Substances 0.000 abstract description 17
- 238000003780 insertion Methods 0.000 abstract description 11
- 230000037431 insertion Effects 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000004913 activation Effects 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 58
- 239000007787 solid Substances 0.000 description 34
- 239000002904 solvent Substances 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- 239000000706 filtrate Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000010898 silica gel chromatography Methods 0.000 description 11
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000001769 aryl amino group Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920006124 polyolefin elastomer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 4
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- MTIDYGLTAOZOGU-UHFFFAOYSA-N 2-bromo-4-methylphenol Chemical compound CC1=CC=C(O)C(Br)=C1 MTIDYGLTAOZOGU-UHFFFAOYSA-N 0.000 description 3
- FFRLMQPMGIMHHQ-UHFFFAOYSA-N 2-bromo-4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(Br)=C1 FFRLMQPMGIMHHQ-UHFFFAOYSA-N 0.000 description 3
- ZDWSNKPLZUXBPE-UHFFFAOYSA-N 3,5-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1 ZDWSNKPLZUXBPE-UHFFFAOYSA-N 0.000 description 3
- FCSKOFQQCWLGMV-UHFFFAOYSA-N 5-{5-[2-chloro-4-(4,5-dihydro-1,3-oxazol-2-yl)phenoxy]pentyl}-3-methylisoxazole Chemical compound O1N=C(C)C=C1CCCCCOC1=CC=C(C=2OCCN=2)C=C1Cl FCSKOFQQCWLGMV-UHFFFAOYSA-N 0.000 description 3
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 3
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- DEFUSPNGFCCTEU-UHFFFAOYSA-N dicyclohexylmethanol Chemical compound C1CCCCC1C(O)C1CCCCC1 DEFUSPNGFCCTEU-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 3
- MKIIBHAVKKVAKM-UHFFFAOYSA-N 1,2-bis(bromomethyl)cyclohexane Chemical compound BrCC1CCCCC1CBr MKIIBHAVKKVAKM-UHFFFAOYSA-N 0.000 description 2
- RJGXLSPAKXWJGN-UHFFFAOYSA-N 2-bromo-4-(3-bromo-4-hydroxyphenyl)phenol Chemical compound C1=C(Br)C(O)=CC=C1C1=CC=C(O)C(Br)=C1 RJGXLSPAKXWJGN-UHFFFAOYSA-N 0.000 description 2
- QSSBFBPOEXRCSX-UHFFFAOYSA-N 2-bromo-6-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(Br)=C(O)C(C(C)(C)C)=C1 QSSBFBPOEXRCSX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000010288 sodium nitrite Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- IDTMQAKXOQZJBT-UHFFFAOYSA-N 1,3-bis(bromomethylidene)cyclohexane Chemical compound C1CC(=CBr)CC(=CBr)C1 IDTMQAKXOQZJBT-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- SOCLAPVGGRUYNS-UHFFFAOYSA-N 2,3-dicyclohexylphenol Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C1CCCCC1 SOCLAPVGGRUYNS-UHFFFAOYSA-N 0.000 description 1
- KUZOHDYKJXNCSI-UHFFFAOYSA-N 2,4-dibromopentane Chemical compound CC(Br)CC(C)Br KUZOHDYKJXNCSI-UHFFFAOYSA-N 0.000 description 1
- LTMSUXSPKZRMAB-UHFFFAOYSA-N 2-bromo-4-methoxyphenol Chemical compound COC1=CC=C(O)C(Br)=C1 LTMSUXSPKZRMAB-UHFFFAOYSA-N 0.000 description 1
- HCMZQOFFKKISQI-UHFFFAOYSA-N 2-chloro-5-(4-chloro-3-hydroxyphenyl)phenol Chemical compound C1=C(Cl)C(O)=CC(C=2C=C(O)C(Cl)=CC=2)=C1 HCMZQOFFKKISQI-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- BPDMSWHVSRHDRZ-UHFFFAOYSA-N 3,5-bis(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C(C)(C)(CC(C)(C)C)C=1C=C(C=C(C1)C(C)(C)CC(C)(C)C)O BPDMSWHVSRHDRZ-UHFFFAOYSA-N 0.000 description 1
- WUUCUKBDERNCLD-UHFFFAOYSA-N 3,5-bis(2,4,6-trimethylphenyl)phenol Chemical compound C1(=C(C(=CC(=C1)C)C)C=1C=C(C=C(C=1)C1=C(C=C(C=C1C)C)C)O)C WUUCUKBDERNCLD-UHFFFAOYSA-N 0.000 description 1
- WYGAQDYPFAVLJF-UHFFFAOYSA-N 3,5-bis(2,6-dimethylphenyl)phenol Chemical compound CC1=C(C(=CC=C1)C)C=1C=C(C=C(C1)C1=C(C=CC=C1C)C)O WYGAQDYPFAVLJF-UHFFFAOYSA-N 0.000 description 1
- DLUMXTSYXVRNIP-UHFFFAOYSA-N 3,5-bis(2-methylpropyl)phenol Chemical compound CC(C)CC1=CC(O)=CC(CC(C)C)=C1 DLUMXTSYXVRNIP-UHFFFAOYSA-N 0.000 description 1
- AGXAAZASECOBCT-UHFFFAOYSA-N 3,5-bis(3,5-ditert-butylphenyl)phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(C=2C=C(C=C(O)C=2)C=2C=C(C=C(C=2)C(C)(C)C)C(C)(C)C)=C1 AGXAAZASECOBCT-UHFFFAOYSA-N 0.000 description 1
- JBNRVNULCTUSLI-UHFFFAOYSA-N 3,5-bis[2,4,6-tri(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC(O)=CC(C=2C(=CC(=CC=2C(C)C)C(C)C)C(C)C)=C1 JBNRVNULCTUSLI-UHFFFAOYSA-N 0.000 description 1
- YYOQJBLGFMMRLJ-UHFFFAOYSA-N 3,5-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC(O)=CC(C(C)C)=C1 YYOQJBLGFMMRLJ-UHFFFAOYSA-N 0.000 description 1
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 1
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 1
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 1
- XJDFBLQCLSBCGQ-UHFFFAOYSA-N anthracene-1-carbaldehyde Chemical compound C1=CC=C2C=C3C(C=O)=CC=CC3=CC2=C1 XJDFBLQCLSBCGQ-UHFFFAOYSA-N 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- UUWSLBWDFJMSFP-UHFFFAOYSA-N bromomethylcyclohexane Chemical compound BrCC1CCCCC1 UUWSLBWDFJMSFP-UHFFFAOYSA-N 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- DWCMDRNGBIZOQL-UHFFFAOYSA-N dimethylazanide;zirconium(4+) Chemical compound [Zr+4].C[N-]C.C[N-]C.C[N-]C.C[N-]C DWCMDRNGBIZOQL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- AFMVESZOYKHDBJ-UHFFFAOYSA-N fluoren-9-ol Chemical compound C1=CC=C2C(O)C3=CC=CC=C3C2=C1 AFMVESZOYKHDBJ-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- KSIFQVHSGOEHQQ-UHFFFAOYSA-J oxolane;tetrachlorohafnium Chemical compound C1CCOC1.C1CCOC1.Cl[Hf](Cl)(Cl)Cl KSIFQVHSGOEHQQ-UHFFFAOYSA-J 0.000 description 1
- LXWBMENBONGPSB-UHFFFAOYSA-J oxolane;tetrachlorotitanium Chemical compound C1CCOC1.C1CCOC1.Cl[Ti](Cl)(Cl)Cl LXWBMENBONGPSB-UHFFFAOYSA-J 0.000 description 1
- VDJJKYYENYIHFF-UHFFFAOYSA-J oxolane;tetrachlorozirconium Chemical compound C1CCOC1.C1CCOC1.Cl[Zr](Cl)(Cl)Cl VDJJKYYENYIHFF-UHFFFAOYSA-J 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Chemical group CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
Description
技术领域
本发明涉及烯烃聚合催化剂技术领域,特别涉及一种四芳氧基IVB族双核金属配合物及其制备和应用。
背景技术
聚烯烃类产品因其原料丰富、价格低廉、便于生产与加工、性能优越等诸多优点,而成为了目前最受人们欢迎的树脂类材料。而目随着人们生活水平的提高,以及一些特殊领域的新需求,高性能聚烯烃尤其是对聚烯烃类弹性体的需求越来越高。聚烯烃弹性体一般是由乙烯和丙烯或者其他α-烯烃(1-丁烯、1-己烯、1-辛烯等)在一定条件下共聚合生成的聚烯烃材料。与通用聚烯烃树脂相比,聚烯烃弹性体分子链内共聚单体的含量高,密度低,具有塑料的可塑性和橡胶的高弹性,广泛应用于汽车零部件、电线电缆、机械工具、密封件、热熔胶等领域。
生产聚烯烃弹性体的核心是催化剂,因此学术界和商业化公司对其进行了大力的开发。茂金属催化剂(如EP0420436B1,US5064802)是目前应用较多的一类催化剂,其对高级α-烯烃同样具有良好的共聚能力,可以实现乙烯/1-丁烯、乙烯/1-己烯、乙烯/1-辛烯的无规共聚,但该催化剂耐温性较差,在工业生产中成本较高,而且获得聚合物分子量相对较低,因此该催化剂用于聚烯烃聚合反应仍有较大改进空间。此外,Dow化学公司还报道了基于亚胺-胺类配体的IVB族金属配合物催化乙烯/α-烯烃共聚合的研究。该类催化剂催化下虽然聚合产物的分子量较高,但1-辛烯的插入率较低。专利CN101484475B公开了一种芳氧基醚骨架的锆配合物,其具有优异的共聚性能和热稳定性(如下式所示,CN101484475B),但聚合产物的分子量仍较低。
发明内容
为了解决上述问题,本发明提出一种四芳氧基IVB族双核金属配合物及其制备和应用。本发明提出的四芳氧基IVB族双核金属配合物用于催化烯烃聚合反应,尤其是烯烃/α-烯烃共聚时表现出非常好的催化活性和热稳定性,并且聚合物分子量较高,有利于提高机械强度,拓宽应用范围。
具体的技术方案如下:
一类四芳氧基IVB族双核金属配合物,其结构如式I或式I’所示:
其中,R1选自氢、卤素、C1-30烷基、C1-30烷氧基、C1-30二烷基氨基、C3-30环烷基、C3-30环烷基氧基、C3-30二环烷基氨基、C6-40芳基或取代芳基、C6-40芳基氧基、C6-40芳基氨基;
R2–R5各自独立地选自氢、卤素、C1-30烷基或环烷基、C1-30烷氧基、C1-30二烷基氨基、C3-30环烷基、C3-30环烷基氧基、C3-30二环烷基氨基、C6-40芳基、C6-40芳基氧基、C6-40芳基氨基、C3-40的三烃基甲硅烷基、C3-40的(三烃基甲硅烷基)烷基;
T1和T2相同或不同,选自除氢原子外具有1至20个原子的二价烃或硅烷基团,或其惰性取代衍生物;
T3和T4相同或不同,选自化学键或除氢原子外具有1至20个原子的二价烃或硅烷基团,或其惰性取代衍生物;
X取代基为一个或两个,当X为两个时,X为除氢以外具有1至20个原子的一价取代基;当X为一个时,X为除氢以外具有1至40个原子的二价取代基。M选自IVB族金属。
优选地,R1选自氢、C1-20烷基或环烷基、C1-20烷氧基、C1-20二烷基氨基、C3-20环烷基、C3-20环烷基氧基、C3-20二环烷基氨基、C6-30芳基或取代芳基、C6-30芳基氧基、C6-30芳基氨基;
优选地,R2–R5相同或不同,各自独立地选自氢、卤素、C1-20烷基、C1-20烷氧基、C1-20二烷基氨基、C3-20环烷基、C3-20环烷基氧基、C3-20二环烷基氨基、C6-30芳基或取代芳基、C6-30芳基氧基、C6-30芳基氨基、C3-30的三烃基甲硅烷基、C3-30的(三烃基甲硅烷基)烷基;
T1和T2相同或不同,选自除氢原子以外具有3至10个原子的二价烃或硅烷基团;
T3和T4相同或不同,选自化学键或除氢原子以外具有1至10个原子的二价烃或硅烷基团,或其惰性取代衍生物;
X取代基为一个或两个,当X为两个时,X为除氢以外具有1至10个原子的一价取代基;当X为一个时,X为除氢以外具有1至20个原子的二价取代基。;
M选自钛、锆、铪。
优选的,R1选自氢、二环己烷基甲基、二苯甲基、二苯并环庚烷基、芴基、咔唑基、蒽基、二环己烷并苯基、3,5-二(叔丁基)苯基、3,5-二(异丙基)苯基、3,5-二(异丁基)苯基、3,5-二(叔辛基)苯基、3,5-二(2,4,6-三甲基苯基)苯基、3,5-二(2,6-二甲基苯基)苯基、3,5-二(2,4,6-三异丙基苯基)苯基、3,5-二(3,5-二叔丁基苯基)苯基;
优选的,R2–R5相同或不同,各自独立地选自氢、卤素、C1-10烷基或环烷基、C1-10烷氧基;
更优选的,R2选自氢、卤素、C1-10烷基或环烷基、C1-10烷氧基;
更优选的,R3–R5自氢;
优选的,T1和T2相同,选自除氢原子外具有3至8个原子的二价烃;
优选的,T3和T4相同,选自化学键或不算氢具有1至8个原子的二价烃或硅烷基团,或其惰性取代衍生物;
优选的,X为两个一价取代基时,选自卤素、甲基、苄基、二甲基氨基、二乙基氨基、苯基、或当X为二价取代基时,X结构选自1,3-丁二烯、1,3戊二烯。它们既表示二烯与M可以直接配位也表示1,4位的两个碳原子与M可以形成共价键;
M选自钛、锆、铪。
一种所述的四芳氧基IVB族双核金属配合物的制备方法,包括以下步骤:
在有机溶剂一中,将如下式II或式II’所示化合物先与拔氢试剂反应生成盐,再与M盐进行络合,反应得到式I或式I’所示配合物;
所述式II或式II’中,R1、R2、R3、R4、R5的定义与式I相同;
优选的,所述M盐为IVB族金属M的卤化物、烷基化合物或氨基化合物中的一种或多种;
优选地,所述拔氢试剂为氢化钠、氢化钾、氢化锂、四甲基乙二胺、双三甲基硅基胺基锂、双三甲基硅基氨基钠、二异丙基胺基锂、C1-C6烷基锂中的一种或多种,更优选为氢化钠、氢化钾、C1-C6烷基锂中的一种或多种;
优选地,所述有机溶剂一为四氢呋喃、无水乙醚、戊烷、环戊烷、正己烷、环己烷、庚烷、甲基环己烷、辛烷、异辛烷、甲苯、二甲苯中的一种或多种;更优选为四氢呋喃、乙醚、正己烷、甲苯。
所述的四芳氧基IVB族双核金属配合物的制备方法,所述式II或式II’所示化合物与拔氢试剂的摩尔比为1:4~8,优选1:4~6;
成盐反应的温度为-78至35℃,优选-78~0℃;
成盐反应的时间为1~24h;
进一步地,所述式II或式II’所示化合物与M盐中金属离子的摩尔比为1:2~3.6,优选1:2~2.6;
络合反应的温度为30至150℃;
络合反应的时间为4~30h。
所述式II或式II’所示化合物是由式III或式III’化合物与质子酸在0~60℃有机溶剂二反应0.5~4h获得;
所述式III或式III’化合物结构式为:
所述式III和式III’中,R1、R2、R3、R4、R5的定义与式I相同,R为羟基保护基,优选二氢吡喃;
优选地,质子酸为盐酸、硫酸、甲酸、乙酸中的一种或多种,所述质子酸的摩尔添加量是式III或式III’化合物的4-16倍,优选5-12倍;
优选地,所述有机溶剂二为乙酸乙酯、甲醇、乙醇中的一种或多种;
所述式III或式III’化合物由以下反应路线和步骤制备:
反应路线各式中R1、R2、R3、R4、R5、T1、T2、T3、T4的定义与式I相同;R为羟基保护基,优选二氢吡喃。
所述式III或式III’化合物的制备方法为:
(1)、在碱金属碳酸盐的催化作用下,在溶剂三中使化合物IV或IV’与化合物V按照摩尔比1:1~1.5加入,40~120℃下回流反应3~12h,分离后得到化合物VI或VI’;所述碱金属碳酸盐的添加量按摩尔量计,为化合物IV或IV’摩尔量的0.1~1.5倍;
优选地,所述化合物V为1,2-二溴乙烷、1,3-二溴丙烷、1,4-二溴丁烷、1,3-二溴苯、2,4-二溴戊烷、1,2-二溴亚甲基-二甲基硅烷、1,3-二(溴亚甲基)环己烷中的一种或多种;
优选地,所述溶剂三为有机溶剂,优选酮类溶剂,更优选丙酮、甲乙酮、甲基异丁基酮、环己酮、异佛尔酮中的一种或多种;
优选地,所述碱金属碳酸盐为碳酸钾、碳酸铯、碳酸锂、碳酸钠中的一种或多种;
(2)、有机溶剂四中,使化合物VI或VI’先与拔氢试剂低温反应成盐,再添加硼酸三异丙酯继续反应,分离后得到化合物VII或VII’;整个过程反应温度为-78至35℃,反应时间为1~6h;
所述化合物VI或VI’、拔氢试剂、硼酸三异丙酯的摩尔比为1:4~6:4~6;
优选地,所述有机溶剂四为四氢呋喃、无水乙醚、戊烷、环戊烷、正己烷、环己烷、庚烷、甲基环己烷、甲苯、二甲苯中的一种或多种;有机溶剂四为超干溶剂。
优选地,所述拔氢试剂为氢化钠、氢化钾、氢化锂、C1-C6烷基锂中的一种或多种,更优选为正丁基锂。
(3)、惰性气氛条件下,将化合物VII或VII’、化合物IX、碱的水溶液在溶剂六中混合后先冻干脱氧,然后加入钯催化剂,在50-120℃下反应36~72h,分离后获得化合物III或III’;所述化合物VII或VII’、化合物IX、碱、四三苯基磷钯的摩尔比为1:4~8:4~10:0.4~1.2;
优选地,所述步骤(3)中的溶剂六为超干有机溶剂,优选乙二醇二甲醚、乙二醇二乙醚、甲苯、乙醚、四氢呋喃的一种或多种的组合物。按照1g反应物,溶剂体积加入量为2-10mL的比例加入,优选1g反应物,溶剂体积加入量为3-8mL。
所述碱优选金属碳酸盐,更优选碳酸钠、碳酸钾、碳酸铯、碳酸锂中的一种或多种;
所述钯催化剂优选四配位的钯催化剂,更优选四(三苯基膦)钯。
进一步的,所述化合物IX的制备方法为:(a)、在对甲苯磺酸吡啶盐的催化作用下,在溶剂五中使2-溴苯酚或其取代衍生物与二氢吡喃在20-60℃下反应4~12h,分离后得到化合物VIII;所述2-溴苯酚或其取代衍生物与二氢吡喃的摩尔比为1:1~2;所述对甲苯磺酸吡啶盐的添加量按摩尔量计,为2-溴苯酚或其取代衍生物摩尔量的0.05~0.5倍;
优选地,所述溶剂五为有机溶剂,优选二氯甲烷、氯仿、四氯乙烷、氯苯中的一种或多种;按照1g反应物,溶剂体积加入量为2-10mL的比例加入,优选1g反应物,溶剂体积加入量为3-8mL。
优选地,2-溴苯酚的取代衍生物为4-甲基-2-溴苯酚、4-叔丁基-2溴苯酚、4-甲氧基-2-溴苯酚中的一种或多种。
(b)、在惰性环境及卤化锡催化剂存在条件下,在溶剂七中使化合物VIII和醇或酚在20-60℃下反应6~24h,分离后得到化合物IX;所述化合物VIII、醇或酚、催化剂的摩尔比为1:1~1.5:0.01~0.1;
优选地,所述溶剂七为有机溶剂,优选二氯甲烷、氯仿、四氯乙烷、氯苯中的一种或多种;按照1g反应物,溶剂体积加入量为2-10mL的比例加入,优选1g反应物,溶剂体积加入量为3-8mL。
优选地,所述醇或酚为二苯甲醇、取代二苯甲醇、二苯并环庚醇、叔丁醇、苯酚、蒽酚、二环己烷基甲醇、芴醇、二环己烷并苯酚、3,5-二(叔丁基)苯酚、3,5-二(异丙基)苯酚、3,5-二(异丁基)苯酚、3,5-二(叔辛基)苯酚、3,5-二(2,4,6-三甲基苯基)苯酚、3,5-二(2,6-二甲基苯基)苯酚、3,5-二(2,4,6-三异丙基苯基)苯酚、3,5-二(3,5-二叔丁基苯基)苯酚中的一种或多种;
优选地,所述卤化锡催化剂为二溴化锡、四溴化锡、二碘化锡、四碘化锡、二氯化锡、四氯化锡中的一种或多种;
进一步地,所述步骤(1)、(2)、(3)、(a)、(b)还分别包括产物分离的工艺;
优选地,所述步骤(1)、(2)、(3)、(a)、(b)各自独立的选用柱层析或重结晶法对产物进行分离提纯。
分离、提纯工艺可选用现有的已知方法进行。
一种四芳氧基IVB族双核金属配合物的应用,所述四芳氧基IVB族双核金属配合物用作烯烃聚合或烯烃/α-烯烃共聚。
进一步地,所述四芳氧基IVB族双核金属配合物用作乙烯/1-辛烯共聚。
所述烯烃聚合或烯烃/α-烯烃共聚反应中还加有助催化剂,所述助催化剂为铝氧烷、烷基铝化合物、氯化烷基铝中的一种或多种的组合物或者是铝氧烷、烷基铝化合物、氯化烷基铝中的一种或多种与一种或多种有机硼化物的组合物。
进一步地所述铝氧烷为甲基铝氧烷(MAO)、改性甲基铝氧烷(MMAO);所述烷基铝化合物为三乙基铝、三异丁基铝、三辛基铝;所述氯化烷基铝为一氯乙基铝、倍半乙基铝、二氯乙基铝;所述有机硼化物为三苯甲基四(五氟苯基)硼酸盐、三(五氟苯基)硼、N,N-二甲基苯胺四(五氟苯基)硼酸盐、双十八烷基甲基叔胺四(五氟苯基)硼酸盐、双氢化牛脂基甲基叔胺四(五氟苯基)硼酸盐。
所述助催化剂中金属铝与催化剂中心金属M的摩尔比Al/M为1–10000;硼与催化剂中心金属M的摩尔比B/M为0-10;聚合温度为20–250℃;聚合压力为0.1–10MPa。
优选地,助催化剂中金属铝与催化剂中心金属M的摩尔比Al/M为3–1000;与催化剂中心金属M的摩尔比B/M为0-4;聚合温度为100–220℃;聚合压力为1–5MPa。
本发明所述四芳氧基IVB族双核金属配合物的加入量为0.05-2μmol/L(每升溶剂和辛烯的总量),本领域技术人员根据反应类型进行适当调整仍在本发明的保护范围内。
本发明提出的四芳氧基IVB族双核金属配合物及其制备和应用原料廉价易得,合成简单。可在助催化剂烷基铝、烷氧基铝或有机硼化物的活化下催化乙烯/α-烯烃共聚,尤其是催化乙烯与高级α-烯烃共聚,如1-辛烯等,催化活性可以达到108g·mol-1(M)·h-1以上,聚合产物的分子量在10000-500000g/mol之间,共单体插入能力在45wt%以上。配合物具有耐温性高、活性高、共单体插入能力强的特点,具有很好的工业应用前景。
具体实施方式
为了方便本领域研究人员更好的知悉本发明,以下将用具体实例进一步描述本发明,但仅为进一步详细描述,并不是限制本发明的范围。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中的浓度如无特别说明,均为摩尔浓度。
下述实施例中所用的材料、试剂等,均可从商业途径得到,具体信息如下:
3,3’-二溴-(1,1’-联苯)-4,4’-二醇,98%,阿拉丁
4,4-二氯-(1,1-联苯)-3,3-二醇,98%,atomax
1,3-二溴丙烷:AR,Innochem
1,2-双(溴甲基)环己烷,98%,Kingchem
碳酸铯:AR,Innochem
丙酮:AR,Innochem
正丁基锂:(1.6mol/L),Innochem
超干四氢呋喃:AR,Innochem
硼酸三异丙酯:AR,Innochem
2-溴-4-叔丁基苯酚:AR,Innochem
二氢吡喃:AR,Innochem
对甲苯磺酸吡啶盐:AR,Aladdin
二氯甲烷:AR,Innochem
二环己基甲醇:(98%),Innochem
四溴化锡:AR,Aldrich
乙二醇二甲醚:AR,Innochem
四三苯基膦钯:AR,Innochem
无水碳酸钠:AR,Innochem
碳酸氢钠:AR,Innochem
无水甲醇:AR,Innochem
乙酸乙酯:AR,Innochem
浓盐酸:AR,Innochem
超干甲苯:AR,Innochem
超干正己烷:AR,Innochem
1,2-双(溴甲基环己烷),98%,Innochem
2-溴-4-甲基苯酚,98%,Innochem
3,5-二叔丁基苯酚,98%,Innochem
双(四氢呋喃)四氯化钛:AR,Alfa
双(四氢呋喃)四氯化锆:AR,Alfa
双(四氢呋喃)四氯化铪:AR,Alfa
甲基溴化镁乙醚溶液,3mol/L,Innochem
石油醚:60–90℃,北京化学试剂公司
4.4'-次甲基-双(2-氯苯胺),98%,Aladdin
亚硝酸钠,99.99%,Innochem
2-溴-6-(叔丁基)-4-甲氧基苯酚,98%,Innochem
氘代氯仿:AR,Acros
工业酒精:95%,北京化学试剂公司
下述实施例中化合物采用核磁共振仪(Brucker ARX-400)进行表征。
下述聚合实施例中所得聚合物的分子量、分子量分布及1-辛烯插入率通过polymer char的GPC-IR测试得到,测试温度为150℃,样品回收率超95%。聚合物熔融峰温度通过DSC测试,采用第二次升温获得的数据,升降温速率为10℃/min。以下内容结合实施例对本发明进行详细说明,但本发明并不限于以下实施例。
下述实施例中配合物的合成按照下述反应方程式进行:
实施例1、化合物1-1的制备
将51.02g 4,4’-二氯-(1,1’-联苯)-3,3’-二醇(0.2mol)溶解于500mL丙酮,加入40.38g 1,3-二溴丙烷(0.2mol,1.0eq.),再加入65.16g碳酸铯(0.2mol,1.0eq.),加热至50℃回流反应12h。过滤除去固体,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=200:1(v/v)),得到48.17g无色固体,产率为81.6%。
化合物1-1的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.22-7.19(t,J=8.0Hz,4H),7.13-7.11(d,J=8.0Hz,2H),7.02(s,4H),4.48(t,J=8.0Hz,8H),2.07(m,4H).13C NMR(CDCl3,100MHz,TMS):δ154.05,143.28,128.78,127.78,123.80,114.40,68.43,30.86.
实施例2、化合物1-2的制备
氮气氛围下,将47.22g(0.08mol)化合物1-1溶解于300mL超干四氢呋喃,体系温度降至-78℃,缓慢滴加200mL正丁基锂(0.32mol,4.0eq.,1.6M)的己烷溶液,-78℃条件下反应3h,再缓慢滴加60.19g硼酸三异丙酯(0.32mol,4.0eq),再反应3h后加30.0mL水淬灭,浓缩反应液,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥,浓缩滤液,加入正己烷重结晶并洗涤,得到37.57g白色固体,产率为74.8%。
化合物1-2的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ8.02(d,J=8.0Hz,4H),7.86(s,4H),7.84(s,4H),7.41(d,J=8.0Hz,4H),6.60(s,8H),4.36(t,J=8.0Hz,8H),1.93(m,4H).13C NMR(CDCl3,100MHz,TMS):δ159.81,143.79,130.64,129.69,121.83,120.70,119.58,118.45,115.59,67.77,32.12.
实施例3、化合物1-3的制备
氮气氛围下,将45.82g(0.2mol)2-溴-4-(叔丁基)苯酚溶于500mL超干二氯甲烷中,然后加入25.236g二氢吡喃(0.3mol,1.5eq.)和5.03g对甲苯磺酸吡啶盐(0.02mol,0.1eq.),30℃下反应6h。二氯甲烷萃取,饱和食盐水水洗,然后合并有机相,用无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=300:1(v/v)),得到55.50g白色固体,产率为88.6%。
化合物1-3的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.58(d,J=8.0Hz,1H),7.22-7.20(dd,J=8.0Hz,1H),7.04(dt,J=8.0Hz,1H),5.42(m,1H),3.88–3.84(m,1H),3.55-3.51(m,1H),2.14-2.10(m,1H),2.05-2.03(m,2H),2.02-2.01(m,1H),1.45–1.40(m,2H),1.22(s,9H).13C NMR(CDCl3,100MHz,TMS):δ152.74,144.83,130.36,125.16,114.62,96.23,61.40,34.10,31.30,30.00,25.10,18.20.
实施例4、化合物1-4的制备
氮气氛围下,分别将50.12g(0.16mol)化合物1-3和31.41g二环己基甲醇(0.16mol,1.0eq.)溶解于500mL超干二氯甲烷,缓慢加入7.01g四溴化锡(0.016mol,0.01eq.),20℃下搅拌24h。加入60mL饱和碳酸氢钠水溶液淬灭反应,二氯甲烷萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=250:1(v/v)),得到71.80g白色固体,产率为91.3%。
化合物1-4的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.36(d,J=8.0Hz,1H),6.99(d,J=8.0Hz,4H),5.54(t,J=8.0Hz,1H),3.85-3.76(dt,J=8.0Hz,2H),2.68(t,J=8.0Hz,1H),2.09(t,J=8.0Hz,2H),2.05(t,J=8.0Hz,2H),1.75-1.62(q,J=8.0Hz,14H),1.44(s,9H),1.39–1.08(m,8H).13C NMR(CDCl3,100MHz,TMS):δ155.31,144.88,128.52,128.26,123.81,113.89,98.19,63.04,50.80,42.66,34.45,34.06,32.06,31.43,30.44,27.50,25.07,24.09,19.59.
实施例5、化合物1-5的制备
分别将18.83g化合物1-2(0.03mol)和59.35g化合物1-4(0.12mol,4..0eq.)溶解于300mL乙二醇二甲醚,再加入40mL碳酸钠水溶液(0.12mol,4.0eq.,3M),液氮冷冻,抽真空除氧,氮气保护下加入13.87g四三苯基磷钯(0.012mol,0.4eq.),50℃下反应72h。浓缩反应液,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=200:1(v/v)),得到44.42g白色固体,产率为71.9%。
化合物1-5的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.69(dt,J=8.0Hz,4H),7.34-7.32(dd,J=8.0Hz,4H),6.94(t,J=8.0Hz,4H),6.93(t,J=8.0Hz,4H),6.92(d,J=8.0Hz,4H),5.53-5.51(dt,J=8.0Hz,4H),4.34(m,8H),3.79-3.73(m,8H),3.00(m,4H),2.12-1.92(m,16H),2.08-2.02(q,J=8.0Hz,4H),1.73-1.62m,56H),1.52(s,36H),1.43(q,J=8.0Hz,8H),135-1.25(m,32H).13C NMR(CDCl3,100MHz,TMS):δ157.08,151.92,143.42,141.64,130.65,130.30,128.74,128.49,127.15,126.17,125.09,114.91,97.95,66.82,62.35,53.60,43.01,36.72,33.27,31.27,31.14,30.77,30.16,27.50,25.07,24.87,18.92.
实施例6、化合物1-6的制备
将41.90g化合物1-5(0.02mol)溶解于120mL乙酸乙酯和120mL甲醇的混合溶液中,再加入8.33mL浓盐酸(0.1mol,5.0eq.,12mol/L),0℃下反应4h。旋干溶剂,得到34.22g白色固体,产率为97.3%。
化合物1-6的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.43(dt,J=8.0Hz,4H),7.14-7.12(dd,J=8.0Hz,4H),6.94(d,J=8.0Hz,4H),6.89(t,J=8.0Hz,4H),6.86(d,J=8.0Hz,4H),5.35(m,4H),4.30(m,8H),3.11(m,4H),2.06-2.02(q,J=8.0Hz,4H),1.73-1.62m,56H),1.55(s,36H),1.35-1.25(m,32H).13C NMR(CDCl3,100MHz,TMS):δ151.92,151.53,143.35,141.43,128.42,127.83,126.53,126.42,125.94,125.67,125.46,114.84,67.02,52.09,42.51,34.10,33.50,31.50,31.28,30.16,27.50,24.59.
实施例7、化合物1-7的制备
在手套箱内,将7.03g化合物1-6(0.004mol)溶解于30mL干燥甲苯,缓慢滴加10mL正丁基锂(0.016mol,4.0eq.,1.6M),-78℃下反应24h后,抽干甲苯,加入15mL干燥正己烷,搅拌15min后静置,过滤并用干燥正己烷洗涤,滤渣加入30mL干燥甲苯溶解,并加入2.67gTiCl4(THF)2(0.008mol,2.0eq.),加热至150℃反应4h,反应结束后过滤,滤液抽干并用干燥正己烷洗涤,滤渣再加入30mL干燥甲苯,过滤收集滤液,抽干溶剂后得到4.64g白色固体,产率为58.3%。
化合物1-7的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.63(dt,J=8.0Hz,4H),7.15-7.13(dd,J=8.0Hz,4H),6.98(d,J=8.0Hz,4H),6.93(t,J=8.0Hz,4H),6.85(d,J=8.0Hz,4H),3.80(m,8H),3.38(m,4H),2.08(q,J=8.0Hz,4H),1.78-1.61(m,56H),1.53(s,36H),1.36-1.22(m,32H).13C NMR(CDCl3,100MHz,TMS):δ158.05,152.19,144.01,142.43,128.64,127.40,127.19,125.99,125.51,122.09,114.96,67.32,49.61,43.31,34.12,33.45,31.65,31.24,30.23,27.58,24.60.
实施例8、化合物1-8的制备
实验步骤基本同实施例7,区别在于:加入3.62g ZrCl4(THF)2(0.0096mol,2.4eq.),得到5.06g灰白色固体,产率为60.8%。
化合物1-8的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.71(dt,J=8.0Hz,4H),7.14(dd,J=8.0Hz,4H),6.95(d,J=8.0Hz,4H),6.90(t,J=8.0Hz,4H),6.86(d,J=8.0Hz,4H),3.84(m,8H),3.36(m,4H),2.10-2.06(q,J=8.0Hz,4H),1.78-1.62(m,56H),1.54(s,36H),135-1.25(m,32H).13C NMR(CDCl3,100MHz,TMS):δ157.48,152.27,144.09,141.59,128.72,127.64,127.27,126.23,125.75,122.00,114.74,67.18,50.95,43.38,34.43,33.56,31.68,31.38,30.56,27.44,24.68.
实施例9、化合物1-9的制备
实验步骤基本同实施例7,区别在于:加入4.83g HfCl4(THF)2(0.0104mol,2.6eq.),得到4.92g灰白色固体,产率为54.6%。
化合物1-9的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.83(dt,J=8.0Hz,4H),7.16(dd,J=8.0Hz,4H),7.02(d,J=8.0Hz,4H),6.98(t,J=8.0Hz,4H),6.89(d,J=8.0Hz,4H),3.88(m,8H),3.46(m,4H),2.12-2.09(q,J=8.0Hz,4H),1.80-1.64(m,56H),1.51(s,36H),13.8-1.27(m,32H).13C NMR(CDCl3,100MHz,TMS):δ157.29,152.35,144.17,140.83,128.62,127.42,127.35,126.01,125.53,121.94,114.39,67.12,50.62,44.31,34.65,33.86,31.75,31.68,30.46,28.24,24.99.
实施例10、化合物2-1的制备
将137.6g 3,3’-二溴-(1,1’-联苯)-4,4’-二醇(0.4mol)溶解于800mL环己酮,加入129.6g 1,2-双(溴甲基)环己烷(0.48mol,1.2eq.),再加入5.53g碳酸钾(0.04mol,0.1eq.),加热回流反应3h。过滤除去固体,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=150:1(v/v)),得到143.50g白色固体,产率为78.9%。
化合物2-1的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.73(d,J=8.0Hz,4H),7.68(dd,J=8.0Hz,4H),7.14-7.11(dd,J=8.0Hz,4H),4.07(q,J=8.0Hz,8H),1.77-1.68(m,12H),1.39-1.24(m,8H).13C NMR(CDCl3,100MHz,TMS):δ152.03,145.12,131.78,131.72,117.09,116.47,67.48,44.49,26.01,24.08.
实施例11、化合物2-2的制备
氮气氛围下,将90.44g(0.1mol)化合物2-1溶解于500mL超干乙醚,体系温度降至0℃,缓慢滴加312.5mL甲基锂(0.5mol,5.0eq.,1.6M)的己烷溶液,0℃条件下反应2h,再缓慢滴加112.86g硼酸三异丙酯(0.6mol,6.0eq),反应1h后缓慢恢复室温后缓慢加100.0mL水淬灭,浓缩反应液,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥,浓缩滤液,加入正己烷重结晶并洗涤,得到58.30g白色固体,产率为76.3%。
化合物2-2的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.91(d,J=8.0Hz,4H),7.48-7.46(dd,J=8.0Hz,2H),7.07-7.05(dd,J=8.0Hz,4H),5.19(bs,8H),4.09(q,J=8.0Hz,8H),1.75-1.60(m,12H),1.38-1.24(m,8H).13C NMR(CDCl3,100MHz,TMS):δ160.44,141.97,135.03,130.79,121.30,117.18,70.13,43.16,26.01,22.49.
实施例12、化合物2-3的制备
氮气氛围下,将74.82g(0.4mol)2-溴-4-甲基苯酚溶于600mL超干四氯乙烷中,然后加入33.65g二氢吡喃(0.4mol,1.0eq.)和5.03g对甲苯磺酸吡啶盐(0.02mol,0.05eq.),60℃下反应6h。二氯甲烷萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=200:1(v/v)),得到94.90g白色固体,产率为87.5%。
化合物2-3的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.29(d,J=8.0Hz,1H),6.99-6.97(dd,J=8.0Hz,1H),6.95-6.92(dd,J=8.0Hz,1H),5.4-5.37(m,1H),3.87–3.50(dm,2H),2.19(t,J=8.0Hz,3H),2.14-1.98(m,4H),1.46-1.35(m,2H).13C NMR(CDCl3,100MHz,TMS):δ151.00,133.20,132.10,128.60,116.40,112.60,96.50,61.40,30.00,25.10,20.00,18.20.
实施例13、化合物2-4的制备
氮气氛围下,分别将65.14g(0.3mol)化合物2-3和74.28g 3,5-二叔丁基苯酚(0.36mol,1.2eq.)溶解于500mL超干四氯乙烷,缓慢加入4.18g二溴化锡(0.015mol,0.05eq.),60℃下搅拌6h。加入100mL饱和碳酸氢钠水溶液淬灭反应,二氯甲烷萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=250:1(v/v)),得到129.02g白色固体,产率为93.6%。
化合物2-4的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.69(q,J=8.0Hz,1H),7.61(dd,J=8.0Hz,2H),7.25(t,J=8.0Hz,2H),5.53-5.52(m,1H),3.82-3.67(m,2H),2.33(t,J=8.0Hz,3H),2.07-2.00(m,4H),1.56(s,18H),1.45–1.38(m,2H).13C NMR(CDCl3,100MHz,TMS):δ150.79,150.02,136.87,134.69,133.12,132.43,129.14,124.73,123.43,118.28,97.31,62.96,34.61,31.33,30.06,24.90,21.75,19.51.
实施例14、化合物2-5的制备
分别将30.56g化合物2-2(0.04mol)和110.27g化合物2-4(0.24mol,6.0eq.)溶解于500mL乙二醇二乙醚,再加入106.67mL碳酸钾水溶液(0.32mol,8.0eq.,3M),液氮冷冻,抽真空除氧,氮气保护下加入36.98g四三苯基磷钯(0.032mol,0.8eq.),加热至120℃回流反应36h。浓缩反应液,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=200:1(v/v)),得到60.82g白色固体,产率为72.3%。
化合物2-5的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.75(dt,J=8.0Hz,4H),7.69(q,J=8.0Hz,4H)7.56(t,J=8.0Hz,8H),7.27-7.25(dd,J=8.0Hz,4H),7.15(dd,J=8.0Hz,4H),7.06(q,J=8.0Hz,4H),6.81(d,J=8.0Hz,4H),5.53-5.50(m,4H),3.97(m,8H),3.76(m,8H),2.36(t,J=8.0Hz,12H),2.05-1.95(m,16H),1.72-1.60(m,12H),1.56(s,72H),1.44-1.40(m,8H),1.31-1.26(m,8H).13C NMR(CDCl3,100MHz,TMS):δ155.09,150.50,147.26,141.58,137.82,134.02,133.34,132.11,128.81,128.53,128.13,126.92,123.87,123.43,122.01,113.17,97.07,69.30,62.27,44.17,34.61,31.33,30.39,26.01,24.87,23.29,20.65,18.84.
实施例15、化合物2-6的制备
将42.06g化合物2-5(0.02mol)溶解于150mL乙酸乙酯和150mL甲醇的混合溶液中,再加入32mL醋酸(0.32mol,16.0eq.,10mol/L),室温反应30min。旋干溶剂,得到33.28g白色固体,产率为94.2%。
化合物2-6的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.70(dt,J=8.0Hz,4H),7.61(q,J=8.0Hz,4H),7.53(dd,J=8.0Hz,8H),7.12(t,J=8.0Hz,4H),7.07(d,J=8.0Hz,4H),7.05(d,J=8.0Hz,4H),6.75(t,J=8.0Hz,4H),5.90(m,4H),3.93(m,8H),2.34(t,J=8.0Hz,12H),1.70-1.60(m,12H),1.56(s,72H),1.34-1.27(m,8H).13C NMR(CDCl3,100MHz,TMS):δ154.96,150.43,142.13,141.37,136.21,131.57,129.56,128.46,127.80,127.51,126.06,124.45,124.33,123.22,121.52,113.10,69.50,44.17,38.54,31.33,26.01,23.29,20.25.
实施例16、化合物2-7的制备
在手套箱内,将7.07g化合物2-6(0.004mol)溶解于30mL干燥甲苯,缓慢滴加15.0mL甲基锂(0.024mol,6.0eq.,1.6M),0℃下反应10h后,抽干甲苯,加入15mL干燥正己烷,搅拌15min后静置,过滤并用干燥正己烷洗涤,滤渣加入30mL干燥甲苯溶解,并加入2.73g TiCl4(0.0144mol,3.6eq.),加热至90℃反应10h,过滤,滤液抽干并用干燥正己烷洗涤,再加入30mL干燥甲苯,过滤收集滤液,抽干溶剂后得到4.54g棕色固体,产率为56.8%。
化合物2-7的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.68(dt,J=8.0Hz,4H),7.58(q,J=8.0Hz,4H),7.54(dd,J=8.0Hz,8H),7.20(t,J=8.0Hz,4H),7.09(d,J=8.0Hz,4H),7.06(d,J=8.0Hz,4H),6.81(t,J=8.0Hz,4H),4.09(m,8H),2.34(t,J=8.0Hz,12H),1.71-1.58(m,12H),1.54(s,72H),1.36-1.28(m,8H).13C NMR(CDCl3,100MHz,TMS):δ155.62,155.34,150.43,141.37,135.78,132.23,129.13,128.46,128.17,127.37,126.38,125.11,123.12,121.09,113.13,69.80,44.15,38.56,31.30,25.91,23.25,20.29.
实施例17、化合物2-8的制备
实验步骤基本同实施例7,区别在于:加入3.32g ZrCl4(THF)2(0.0088mol,2.2eq.),得到5.27g灰白色固体,产率为63.1%。
化合物2-8的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.72(dt,J=8.0Hz,4H),7.65(q,J=8.0Hz,4H),7.53(dd,J=8.0Hz,8H),7.28(t,J=8.0Hz,4H),7.12(d,J=8.0Hz,4H),7.08(d,J=8.0Hz,4H),6.72(t,J=8.0Hz,4H),4.02(m,8H),2.37(t,J=8.0Hz,12H),1.68(m,12H),1.56(s,72H),1.39-1.31(m,8H).13C NMR(CDCl3,100MHz,TMS):δ155.70,154.77,150.34,141.32,136.02,132.31,129.37,12856,128.36,128.25,127.61,126.29,125.19,123.42,121.33,113.18,69.46,44.17,38.66,31.27,25.56,23.35,20.25.
实施例18、化合物2-9的制备
实验步骤基本同实施例7,区别在于:加入4.09g HfCl4(THF)2(0.0088mol,2.2eq.),得到5.26g灰白色固体,产率为58.2%。
化合物2-9的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.76(dt,J=8.0Hz,4H),7.67(q,J=8.0Hz,4H),7.58(dd,J=8.0Hz,8H),7.16(t,J=8.0Hz,4H),7.04(d,J=8.0Hz,4H),7.01(d,J=8.0Hz,4H),6.68(t,J=8.0Hz,4H),4.12(m,8H),2.31(t,J=8.0Hz,12H),1.73-1.60(m,12H),1.56(s,72H),1.35-1.27(m,8H).13C NMR(CDCl3,100MHz,TMS):δ155.78,154.58,150.72,141.39,135.80,132.39,129.15,128.86,128.33,128.23,127.39,126.22,125.27,123.22,121.11,113.23,69.43,44.31,38.23,31.20,26.09,23.38,20.45.
实施例19、化合物2-10的制备
在手套箱中,将2.0g化合物2-7(0.001mol)溶解于30mL乙醚中,缓慢滴加1.47mL甲基溴化镁乙醚溶液(0.0044mol,4.4eq.,3M),室温搅拌反应6h,抽干乙醚,加入30mL超干甲苯,搅拌10min,过滤,收集滤液。将滤液抽干,加入5mL己烷洗涤两次,再次过滤,抽干滤渣,获得1.56g浅褐色固体,产率为81.2%。
化合物2-10核磁结果:1H NMR(CDCl3,400MHz,TMS):δ7.72(dt,J=8.0Hz,4H),7.63(q,J=8.0Hz,4H),7.50(dd,J=8.0Hz,8H),7.14(t,J=8.0Hz,4H),7.03(d,J=8.0Hz,4H),7.02(d,J=8.0Hz,4H),6.81(d,J=8.0Hz,4H),4.22(m,8H),2.41(t,J=8.0Hz,12H),2.30(s,12H),1.73-1.50(m,12H),1.61(s,72H),1.31-1.24(m,8H).13C NMR(CDCl3,100MHz,TMS):δ158.59,155.18,150.76,141.87,136.28,131.79,130.66,129.63,128.46,127.87,127.73,127.33,124.67,123.16,121.59,113.40,71.89,66.50,46.17,35.56,30.33,27.12,23.48,20.29.
实施例20、化合物2-11的制备
实验步骤基本同实施例19,区别在于:将2.09g化合物2-8(0.001mol)溶解于30mL乙醚中,得到1.69g白色固体,产率为84.4%。
化合物2-11核磁结果:1H NMR(CDCl3,400MHz,TMS):δ7.81(dt,J=8.0Hz,4H),7.76(q,J=8.0Hz,4H),7.61(dd,J=8.0Hz,8H),7.24(t,J=8.0Hz,4H),7.13(d,J=8.0Hz,4H),7.08(d,J=8.0Hz,4H),6.77(d,J=8.0Hz,4H),4.18(m,8H),2.58(t,J=8.0Hz,12H),2.40(s,12H),1.78-1.62(m,12H),1.59(s,72H),1.29-1.21(m,8H).13C NMR(CDCl3,100MHz,TMS):δ158.02,155.26,151.23,143.37,136.52,131.87,130.57,129.87,128.86,128.11,127.81,124.75,123.92,121.83,116.08,67.50,45.87,41.05,37.96,33.63,26.96,24.29,20.25.
实施例21、化合物2-12的制备
实验步骤基本同实施例19,区别在于:将2.26g化合物2-9(0.001mol)溶解于30mL乙醚中,得到1.76g白色固体,产率为80.6%。
化合物2-12核磁结果:1H NMR(CDCl3,400MHz,TMS):δ7.65(dt,J=8.0Hz,4H),7.57(q,J=8.0Hz,4H),7.45(dd,J=8.0Hz,8H),7.21(t,J=8.0Hz,4H),7.07(d,J=8.0Hz,4H),6.98(d,J=8.0Hz,4H),6.82(d,J=8.0Hz,4H),4.32(m,8H),2.44(t,J=8.0Hz,12H),2.37(s,12H),1.82-1.60(m,12H),1.58(s,72H),1.33-1.22(m,8H).13C NMR(CDCl3,100MHz,TMS):δ157.83,155.34,152.03,142.37,136.30,131.95,130.44,129.65,128.76,127.89,127.17,124.83,123.63,121.61,114.10,72.50,45.17,43.05,39.64,32.83,28.51,22.79,21.01.
实施例22、化合物3-1的制备
冰水浴中,将160.29g(0.6mol)4,4'-亚甲基双(2-氯苯胺)加入到500mL乙醇中,加入51.75g(0.75mol,1.25eq.)亚硝酸钠,开启搅拌。然后缓慢滴加入300mL稀盐酸溶液(1.5mol,2.5eq.,5mol/L),搅拌反应10h。然后加入300mL硫酸溶液(0.9mol,1.5eq.,3mol/L)加热至70℃反应6h。加入碳酸氢钠将溶液调至中性,旋蒸除掉乙醇,然后加入乙酸乙酯进行萃取,收集有机相,旋干溶剂,重结晶后获得化合物3-1共132.89g,收率82.3%。
化合物3-1核磁结果:1H NMR(CDCl3,400MHz,TMS):δ7.19(t,J=8.0Hz,2H),7.11(dt,J=8.0Hz,2H),6.89(dd,J=8.0Hz,2H),5.74(s,2H),3.82(t,J=8.0Hz,2H).13C NMR(CDCl3,100MHz,TMS):δ151.45,133.69,130.61,129.07,120.24,116.78,40.40.
实施例23、化合物3-2的制备
将107.65g 3-1(0.4mol)溶解于800mL丙酮,加入121.13g 1,3-二溴丙烷(0.6mol,1.5eq.),再加入195.49g碳酸铯(0.6mol,1.5eq.),加热至70℃回流反应7h。过滤除去固体,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=200:1(v/v)),得到102.90g无色固体,产率为83.2%。
化合物3-2的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.04(dt,J=8.0Hz,4H),6.88(s,4H),7.02(s,4H),6.72(dd,J=8.0Hz,4H),3.99(m,8H),3.69(m,4H),2.20(m,4H).13C NMR(CDCl3,100MHz,TMS):δ153.84,131.45,129.66,128.92,124.35,114.43,68.70,39.14,31.66.
实施例24、化合物3-3的制备
氮气氛围下,将61.84g(0.1mol)化合物3-2溶解于500mL超干THF中,体系温度降至0℃,缓慢滴加375mL甲基锂(0.6mol,6.0eq.,1.6M)的己烷溶液,30℃条件下反应0.5h,再缓慢滴加94.05g硼酸三异丙酯(0.5mol,5.0eq),反应0.5h后缓慢恢复室温后缓慢加100.0mL水淬灭,浓缩反应液,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥,浓缩滤液,加入正己烷重结晶并洗涤,得到49.78g白色固体,产率为75.9%。
化合物3-3的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.48(s,4H),7.02(d,J=8.0Hz,4H),6.85(dd,J=8.0Hz,4H),5.28(bs,8H),3.87(m,8H),3.77(m,4H),2.06(m,4H).13C NMR(CDCl3,100MHz,TMS):δ161.64,134.73,131.74,130.59,120.49,114.64,68.04,42.20,32.92.
实施例25、化合物3-4的制备
氮气氛围下,将103.66g(0.4mol)2-溴-6-(叔丁基)-4-甲氧基苯酚溶于600mL超干四氯乙烷中,然后加入67.30g二氢吡喃(0.8mol,2.0eq.)和50.26g对甲苯磺酸吡啶盐(0.2mol,0.5eq.),50℃下反应4h。乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=150:1(v/v)),得到110.67g白色固体,产率为80.6%。
化合物3-4的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.12(t,J=8.0Hz,1H),6.80(dd,J=8.0Hz,1H),5.42(d,J=8.0Hz,1H),3.83(s,3H),3.81(m,1H),3.75(m,1H),2.12(m,2H),2.05(m,2H),1.43(m,2H),1.39(s,9H).13C NMR(CDCl3,100MHz,TMS):δ154.95,152.47,140.02,116.68,116.48,112.41,95.79,62.56,55.36,31.71,30.12,30.04,24.90,19.11.
实施例26、化合物3-5的制备
分别将26.23g化合物3-3(0.04mol)和109.84g化合物3-4(0.32mol,8.0eq.)溶解于400mL乙二醇二乙醚,再加入133.33mL碳酸钾水溶液(0.4mol,10.0eq.,3M),液氮冷冻,抽真空除氧,氮气保护下加入55.47g四三苯基磷钯(0.048mol,1.2eq.),加热至80℃反应48h。浓缩反应液,乙酸乙酯萃取,饱和食盐水水洗,有机相合并,无水硫酸钠干燥。滤液浓缩后经硅胶柱层析纯化(石油醚:乙酸乙酯=200:1(v/v)),得到45.21g白色固体,产率为74.6%。
化合物3-5的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.14(s,4H),6.87(s,4H)6.85(d,J=8.0Hz,8H),6.79(d,J=8.0Hz,4H),6.48(s,4H),5.42(m,4H),3.91(m,4H),3.81(m,12H),3.79(m,8H),3.75(m,4H),3.74(m,4H),2.18(t,J=8.0Hz,4H),2.09(m,8H),2.01(m,8H),1.43(m,4H),1.34(s,36H).13C NMR(CDCl3,100MHz,TMS):δ155.58,152.96,147.63,137.35,130.61,129.41,129.41,125.47,125.01,112.62,111.59,95.55,67.09,61.87,55.98,38.88,33.85,30.96,30.37,29.87,24.87,18.44.
实施例27、化合物3-6的制备
将30.30g化合物3-5(0.02mol)溶解于100mL乙酸乙酯和100mL甲醇的混合溶液中,再加入16.67mL浓盐酸(0.2mol,10.0eq.,12mol/L),室温反应2h。旋干溶剂,得到22.37g白色固体,产率为93.7%。
化合物3-6的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.06(s,4H),6.79(d,J=8.0Hz,8H),6.73(d,J=8.0Hz,4H),6.40(s,4H),5.35(s,4H),3.82(s,12H),3.75(m,8H),3.65(s,4H),2.18(m,4H),1.37(s,36H).13C NMR(CDCl3,100MHz,TMS):δ154.36,153.24,143.00,135.74,130.74,.129.26,129.00,126.89,125.85,124.96,112.55,110.81,67.29,56.12,38.46,33.78,30.96,30.00.
实施例28、化合物3-7的制备
在手套箱内,将4.77g化合物3-6(0.004mol)溶解于30mL干燥甲苯,缓慢滴加20.0mL甲基锂(0.032mol,8.0eq.,1.6M),30℃下反应1h后,抽干甲苯,加入15mL干燥正己烷,搅拌15min后静置,过滤并用干燥正己烷洗涤,滤渣加入30mL干燥甲苯溶解,并加入2.57g四(二甲氨基)锆(0.0096mol,2.4eq.),30℃反应30h,过滤,滤液抽干并用干燥正己烷洗涤,再加入30mL干燥甲苯,过滤收集滤液,抽干溶剂后得到3.24g白色固体,产率为52.3%。
化合物3-7的核磁结构:1H NMR(CDCl3,400MHz,TMS):δ7.09(s,4H),6.83(d,J=8.0Hz,4H),6.79(d,J=8.0Hz,4H),6.73(d,J=8.0Hz,4H),6.37(s,4H),3.82(s,12H),3.72(m,8H),3.60(m,4H),2.30(s,24H),2.14(m,4H),1.33(s,36H).13C NMR(CDCl3,100MHz,TMS):δ153.36,152.24,149.96,135.42,130.54,129.89,126.48,125.89,122.09,112.55,111.50,67.29,56.12,38.46,30.96,30.19,26.82,26.68.
实施例29-45、分别利用化合物1-7/MMAO,1-8/MMAO,1-9MMAO,2-7/MMAO,2-8/MMAO,2-9/MMAO,2-10/MMAO,2-11/MMAO,2-12/MMAO,3-7/MMAO体系催化乙烯/1-辛烯聚合
在2L反应釜中加入干燥后的IsoparE溶剂0.8L,升温至140℃,搅拌30min清洗反应釜。冷却至室温将溶剂放出。然后升温至140℃抽真空干燥30min。期间不断用氮气置换。反应釜冷却至80℃以下,向反应釜中加入0.8L IsoparE和0.2L 1-辛烯,除实施例30加入1μmol外,其他实施例加入0.25μmol上面合成的金属化合物,按照Al/M加入一定量的MMAO。升温至设定温度(聚合温度)后通入3MPa乙烯开始聚合反应,反应6min。然后将乙烯放空,将反应液放至乙醇中,收集析出的固体,在60℃真空干燥箱中干燥至恒重后称量,并进行样品分析。
表1化合物/MMAO体系催化乙烯/1-辛烯聚合数据表
a:1-辛烯插入率,wt%,质量百分数。
实施例46、利用化合物2-11/MAO体系催化乙烯/1-辛烯共聚
在2L反应釜中加入干燥后的IsoparE溶剂0.8L,升温至140℃,搅拌30min清洗反应釜。冷却至室温将溶剂放出。然后升温至140℃抽真空干燥30min。期间不断用氮气置换。反应釜冷却至80℃以下,向反应釜中加入0.8L IsoparE和0.2L 1-辛烯,加入0.25μmol化合物2-11,按照Al/Zr=120,加入一定量的MAO。升温至175℃,后通入3MPa乙烯开始聚合反应,反应6min。然后将乙烯放空,将反应液放至乙醇中,收集析出的固体,在60℃真空干燥箱中干燥至恒重后称量,并进行样品分析。共获得200.5g聚合物,活性为4.01×108g/molM,Mw=20.6×104g/mol,PDI=2.4,1-辛烯插入率为51.6%,Tm=48.7℃。
实施例47-53、利用化合物2-11/烷基铝或烷氧基铝/有机硼化物体系催化乙烯/1-辛烯聚合
在2L反应釜中加入干燥后的IsoparE溶剂0.8L,升温至140℃,搅拌30min清洗反应釜。冷却至室温将溶剂放出。然后升温至140℃抽真空干燥30min。期间不断用氮气置换。反应釜冷却至80℃以下,向反应釜中加入0.8L IsoparE和0.2L 1-辛烯,除实施例53加入0.06μmol外其他实施例加入0.125μmol上面合成的金属化合物,按照Al/M加入一定量的烷基铝或烷氧基铝,按照B/M加入一定量的有机硼化物。升温至180℃后通入3MPa乙烯开始聚合反应,反应6min。然后将乙烯放空,将反应液放至乙醇中,收集析出的固体,在60℃真空干燥箱中干燥至恒重后称量,并进行样品分析。
表2化合物2-11/烷基铝或烷氧基铝/有机硼化物体系催化乙烯/1-辛烯聚合数据表
a:B1指三苯甲基四(五氟苯基)硼酸盐,B2表示N,N-二甲基四(五氟苯基)硼酸盐,B3表示双十八烷基甲基叔胺四(五氟苯基)硼酸盐;b:1-辛烯插入率,wt%,质量百分数。
实施例54、利用化合物2-11/MMAO/1-己烯聚合
在2L反应釜中加入干燥后的IsoparE溶剂0.8L,升温至140℃,搅拌30min清洗反应釜。冷却至室温将溶剂放出。然后升温至140℃抽真空干燥30min。期间不断用氮气置换。反应釜冷却至80℃以下,向反应釜中加入0.8L IsoparE和0.2L 1-己烯,加入0.25μmol化合物2-11,按照Al/M=400加入MMAO溶液,升温至160℃后通入3MPa乙烯开始聚合反应,反应6min。然后将乙烯放空,将反应液放至乙醇中,收集析出的固体,在60℃真空干燥箱中干燥至恒重后称量,共获得210.8g聚合物,活性为4.21×108g/molM,Mw=23.2×104g/mol,PDI=2.4,1-辛烯插入率为53.6%,Tm=49.7℃。
对比例1、仅使用MMAO催化乙烯/1-辛烯聚合
聚合反应过程基本与实施例29相同,区别在于:体系内不加入化合物1-7,未得到任何聚合物,反应体系无活性。
对比例2、仅使用MMAO/有基硼催化乙烯/1-辛烯聚合
聚合反应过程基本与实施例47相同,区别在于:体系内不加入化合物2-11,未得到任何聚合物,反应体系无活性。
对比例3、仅使用iBu3Al/有基硼催化乙烯/1-辛烯聚合
聚合反应过程基本与实施例49相同,区别在于:体系内不加入化合物2-11,未得到任何聚合物,反应体系无活性。
对比例4、仅使用MMAO催化乙烯/1-己烯聚合
聚合反应过程基本与实施例54相同,区别在于:体系内不加入化合物2-11,未得到任何聚合物,反应体系无活性。
对比例5、参考专利CN101484475B中实施例3的方法制备如下结构化合物(Zr0),用于催化乙烯/1-辛烯共聚
聚合实验步骤基本同实施例43,区别在于:体系内加入以配合物Zr0(0.5μmol)为主催化剂,得到132.4g聚合物,活性为2.64×108g/mol,Mw=7.9×104g/mol,PDI=2.4,1-辛烯插入率为49%,Tm=56℃
由上述测试结果可知,选用本发明提供的配合物作为主催化剂,结合助催化剂组成的催化剂组合物,能表现出较高的烯烃均聚或共聚活性,产物的分子量高,并且具有较高的热稳定性,适用于较高反应温度的聚合体系。
以上对本发明的实施方式进行了具体说明,但是本发明不限于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (27)
2.根据权利要求1所述的一种四芳氧基IVB族双核金属配合物,其特征在于,R1选自C1-20烷基、C3-20环烷基、3,5-二(叔丁基)苯基;
R2选自C1-20烷基、C1-20烷氧基;R3-R5选为氢;
T1和T2相同或不同,选自除氢原子以外具有3至10个原子的二价烃;
T3和T4相同或不同,选自化学键或除氢原子以外具有1至10个原子的二价烃;
X取代基选自卤素、二甲基氨基、二乙基氨基;
M选自钛、锆、铪。
3.根据权利要求2所述的一种四芳氧基IVB族双核金属配合物,其特征在于,R1选自二环己烷基甲基、二苯甲基、3,5-二(叔丁基)苯基、3,5-二(异丙基)苯基、3,5-二(异丁基)苯基、3,5-二(叔辛基)苯基;
R2选自C1-10烷基、C1-10烷氧基;
R3–R5自氢;
T1和T2相同,选自除氢原子外具有3至8个原子的二价烃;
T3和T4相同,选自化学键或除氢原子外具有1至8个原子的二价烃。
5.根据权利要求4所述的制备方法,其特征在于,所述拔氢试剂为氢化钠、氢化钾、氢化锂、四甲基乙二胺、双三甲基硅基胺基锂、双三甲基硅基氨基钠、二异丙基胺基锂、C1-C6烷基锂中的一种或多种。
6.根据权利要求5所述的制备方法,其特征在于,所述拔氢试剂为氢化钠、氢化钾、C1-C6烷基锂中的一种或多种。
7.根据权利要求4所述的制备方法,其特征在于,所述有机溶剂一为四氢呋喃、无水乙醚、戊烷、环戊烷、正己烷、环己烷、庚烷、甲基环己烷、辛烷、异辛烷、甲苯、二甲苯中的一种或多种。
8.根据权利要求7所述的制备方法,其特征在于,所述有机溶剂一为四氢呋喃、乙醚、正己烷、甲苯。
9.根据权利要求4所述的制备方法,其特征在于,所述式II或式II’所示化合物与拔氢试剂的摩尔比为1:4~8。
10.根据权利要求9所述的制备方法,其特征在于,所述式II或式II’所示化合物与拔氢试剂的摩尔比为1:4~6。
11.根据权利要求4所述的制备方法,其特征在于,成盐反应的温度为-78至35℃。
12.根据权利要求11所述的制备方法,其特征在于,成盐反应的温度为-78~0℃。
13.根据权利要求4所述的制备方法,其特征在于,成盐反应的时间为1~24h。
14.根据权利要求4所述的制备方法,其特征在于,所述式II或式II’所示化合物与M盐中金属离子的摩尔比为1:2~3.6。
15.根据权利要求14所述的制备方法,其特征在于,所述式II或式II’所示化合物与M盐中金属离子的摩尔比为1:2~2.6。
16.根据权利要求4所述的制备方法,其特征在于,络合反应的温度为30至150℃;
络合反应的时间为4~30h。
18.根据权利要求17所述的制备方法,其特征在于,R为二氢吡喃。
19.根据权利要求17所述的制备方法,其特征在于,质子酸为盐酸、硫酸、甲酸、乙酸中的一种或多种,所述质子酸的摩尔添加量是式III或式III’化合物的4-16倍。
20.根据权利要求19所述的制备方法,其特征在于,所述质子酸的摩尔添加量是式III或式III’化合物的5-12倍。
21.根据权利要求17所述的制备方法,其特征在于,所述有机溶剂二为乙酸乙酯、甲醇、乙醇中的一种或多种。
22.根据权利要求1所述的一种四芳氧基IVB族双核金属配合物的应用,其特征在于:所述四芳氧基IVB族双核金属配合物用作烯烃聚合或烯烃/α-烯烃共聚。
23.根据权利要求22所述的一种四芳氧基IVB族双核金属配合物的应用,其特征在于:所述四芳氧基IVB族双核金属配合物用作乙烯/1-辛烯共聚。
24.根据权利要求22所述的一种四芳氧基IVB族双核金属配合物的应用,其特征在于:所述烯烃聚合或烯烃/α-烯烃共聚反应中还加有助催化剂,所述助催化剂为铝氧烷、烷基铝化合物、氯化烷基铝中的一种或多种的组合物或者是铝氧烷、烷基铝化合物、氯化烷基铝中的一种或多种与一种或多种有机硼化物的组合物。
25.根据权利要求24所述的一种四芳氧基IVB族双核金属配合物的应用,其特征在于:所述铝氧烷为甲基铝氧烷、改性甲基铝氧烷;所述烷基铝化合物为三乙基铝、三异丁基铝、三辛基铝;所述氯化烷基铝为一氯乙基铝、倍半乙基铝、二氯乙基铝;所述有机硼化物为三苯甲基四(五氟苯基)硼酸盐、三(五氟苯基)硼、N,N-二甲基苯胺四(五氟苯基)硼酸盐、双十八烷基甲基叔胺四(五氟苯基)硼酸盐、双氢化牛脂基甲基叔胺四(五氟苯基)硼酸盐。
26.根据权利要求24或25所述的一种四芳氧基IVB族双核金属配合物的应用,其特征在于:助催化剂中金属铝与催化剂中心金属M的摩尔比Al/M为1–10000;硼与催化剂中心金属M的摩尔比B/M为0-10;聚合温度为20–250℃;聚合压力为0.1–10MPa。
27.根据权利要求26所述的一种四芳氧基IVB族双核金属配合物的应用,其特征在于:助催化剂中金属铝与催化剂中心金属M的摩尔比Al/M为3–1000;与催化剂中心金属M的摩尔比B/M为0-4;聚合温度为100–220℃;聚合压力为1–5MPa。
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