CN114195706A - 一种n-三苯基亚胺吡啶配体及其镍和钯配合物及配合物的制备与应用 - Google Patents
一种n-三苯基亚胺吡啶配体及其镍和钯配合物及配合物的制备与应用 Download PDFInfo
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- CN114195706A CN114195706A CN202111259158.7A CN202111259158A CN114195706A CN 114195706 A CN114195706 A CN 114195706A CN 202111259158 A CN202111259158 A CN 202111259158A CN 114195706 A CN114195706 A CN 114195706A
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- Prior art keywords
- triphenylimine
- pyridine
- complex
- triphenyliminepyridine
- palladium
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 108
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 104
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003446 ligand Substances 0.000 title claims abstract description 38
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 37
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 28
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 28
- 229920000098 polyolefin Polymers 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- SSDIIKNSUCERSG-UHFFFAOYSA-N nickel;pyridine Chemical compound [Ni].C1=CC=NC=C1 SSDIIKNSUCERSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 239000004711 α-olefin Substances 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 238000003780 insertion Methods 0.000 claims description 13
- 230000037431 insertion Effects 0.000 claims description 13
- 238000007334 copolymerization reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 150000002816 nickel compounds Chemical class 0.000 claims description 7
- 239000012074 organic phase Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000002941 palladium compounds Chemical class 0.000 claims description 6
- 239000000039 congener Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- ATDIROHVRVQMRO-UHFFFAOYSA-N 2,6-dibromo-4-methylaniline Chemical compound CC1=CC(Br)=C(N)C(Br)=C1 ATDIROHVRVQMRO-UHFFFAOYSA-N 0.000 claims description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [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 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 25
- 239000005977 Ethylene Substances 0.000 abstract description 25
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 51
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- 238000001819 mass spectrum Methods 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 229920000573 polyethylene Polymers 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
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- 239000000178 monomer Substances 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 238000006384 oligomerization reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- JLENAYQUNJXNAF-UHFFFAOYSA-N 4-methyl-2,6-diphenylaniline Chemical compound NC=1C(C=2C=CC=CC=2)=CC(C)=CC=1C1=CC=CC=C1 JLENAYQUNJXNAF-UHFFFAOYSA-N 0.000 description 5
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 238000010516 chain-walking reaction Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- UWONEVBFSGKQAJ-UHFFFAOYSA-N nickel(2+);pyridine Chemical compound [Ni+2].C1=CC=NC=C1 UWONEVBFSGKQAJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
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- 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
技术领域
本发明属于乙烯聚合催化技术领域,具体涉及一种N-三苯基亚胺吡啶配体及其镍和钯配合物及镍和钯配合物的制备与应用。
技术背景
由于独特的低粘度、低密度、良好的流变性及末端可功能化修饰等优点,高支化乙烯低聚物在很多领域都有广泛的应用,如作为润滑剂、增韧剂、增溶剂、交联剂、表面改性剂等,作为功能性添加剂具有很高的附加值。具有超支化微结构的低分子量乙烯低聚物通常很难通过传统的催化工艺制备。传统多活性中心的Ziegler-Natta催化体系特点是所制备的支化聚乙烯通常支链较短,且支链分布不均一,分子量分布较宽。
聚α-烯烃合成润滑油具有优异的黏温性能和低温流动性,但主要存在工艺流程复杂、原料价格高和目标产物收率较低,导致生产成本居高不下。如果能采用廉价的原料如丙烯、乙烯,通过开发新型催化剂,直接低聚生产聚烯烃润滑油,不仅能简化合成工艺,降低生产成本,还能减少环境污染,提高聚乙烯材料的附加值。自从Brookhart教授研究发现α-二亚胺钯催化剂具有超强的链行走能力,能够催化乙烯链行走聚合能得到超支化、油状的聚乙烯产物。但是产物的黏度太高,低温流动性差,使得早期所得HBPE只能用作润滑油的黏度指数改进剂。虽然利用α-二亚胺钯催化乙烯低聚直接制备了油状的HBPE,并且具有合成润滑油应用的前景,但是也存在一些问题。首先,产物聚乙烯油的低温流动性有待进一步提高。其次,产物的支化结构以甲基短支链为主,长支链含量低,与相同分子量的聚α-烯烃润滑油相比粘度指数偏低。
为改善聚烯烃材料的表面性、混溶性,黏附力、流变性及与其它高分子材料的相容性和共混性等重要性能,将极性基团引入到聚烯烃链结构中,拓宽聚烯烃的功能,增加聚烯烃的价值,成为烯烃聚合领域的重要研究方向。
工业上目前广泛研究与应用的前过渡金属催化剂不能够催化烯烃与极性单体共聚,主要是因为极性官能团容易毒化金属中心,如氧,氮,膦等杂原子,使催化剂失活。极性单体的存在易于形成极性基团螯合与加快链转移反应,导致共聚反应活性低、极性单体插入率低、以及聚合物分子量低等问题。
发明内容
为了解决上述问题,本发明的目的之一在于提供一种N-三苯基亚胺吡啶配体,该N-三苯基亚胺吡啶配体的结构式如式(Ⅰ)所示:
其中,R为氢-H、甲基-CH3、氯-Cl、氟-F和叔丁基-tBu中任意一种。
本发明还提供上述一种N-三苯基亚胺吡啶配体的制备方法,包括以下步骤:
S1.在圆底烧瓶中放入0.5-4N的ZnCl2、10-50N的2-乙酰吡啶和3-10mL 冰醋酸的悬浮液,加入0.8-3N的2,6-二-(4-R-苯基)-4-甲基苯胺同类物,加热搅拌回流1-6h,冷却至室温;N为当量值;
S2.S1中溶液冷却至室温,沉淀出亮黄色固体,过滤并分离所述亮黄色固体,依次使用乙酸和乙醚洗涤后,在真空下干燥得到橘红色提纯固体;
S3.将所述橘红色提纯固体放入盛有10-60mL二氯甲烷的圆底烧瓶中,加入1-6N草酸钾水溶液3-20mL,并以1000-2000r/min速度搅拌30-80min;
S4.搅拌后溶液进行两相分离,水洗有机溶剂层,并用MgSO4干燥除去有机溶剂层水,再减压过滤;
S5.过滤后在真空干燥箱中去除溶剂,得到产物为黄色粉末或黄色油性产物,即为所需的N-三苯基亚胺吡啶配体。
该制备方法的反应过程为:
优选的,所述2,6-二-(4-R-苯基)-4-甲基苯胺同类物的制备方法,具体步骤为:
S11.氮气气氛下,将10-30N的4-R-苯基硼酸、5-20N的2,6-二溴-4-甲基-苯胺、1-2N的Pd(PPh3)4和30-100N的K2 CO3的混合物加入四氢呋喃与水的混合物液中,再将混合物液加热至65-80℃,搅拌18-36h;四氢呋喃与水以4:1~6:1体积比混合;
S12.将反应后的混合物液转移到旋转蒸发器中,去除溶剂,并用二氯甲烷提取残渣,继续转移到分液漏斗,加入水,震荡后静置分离出下层有机相,并用MgSO4干燥所述有机相;
S13过滤除去MgSO4固体,将有机相转移到旋转蒸发器中浓缩,浓缩液通过硅胶柱层析(硅胶:PE/DCM=1:1)分离,分离得到的第二个白色组分即为2,6-二-(4-R-苯基)-4-甲基苯胺同类物。
本发明的目的之二在于提供一种N-三苯基亚胺吡啶镍配合物,所述配合物由上述的N-三苯基亚胺吡啶配体与镍化合物形成,所述镍化合物为 (DME)NiBr2,所述配合物的结构式如式(Ⅱ)所示:
其中,R为氢-H、甲基-CH3、氯-Cl、氟-F和叔丁基-tBu中任意一种。
优选的,N-三苯基亚胺吡啶镍配合物制备方法为:在氮气氛围下,将N-三苯基亚胺吡啶配体和(DME)NiBr2按摩尔比1:0.5-2混合并溶解在惰性溶剂中,室温下搅拌反应6-24h;搅拌结束后,在旋转蒸发器皿中采用减压蒸馏方式得到固体产物,并将所述固体产物用乙烷洗涤,真空干燥得到所需的N-三苯基亚胺吡啶镍配合物。
反应过程如下:
优选的,所述惰性溶剂为二氯甲烷或三氯甲烷。
本发明的目的之三在于提供一种N-三苯基亚胺吡啶钯配合物,所述配合物由上述的N-三苯基亚胺吡啶配体与钯化合物形成,所述钯化合物为 (COD)PdMeCl,所述配合物的结构式如式(Ⅲ)所示:
其中,R为氢-H、甲基-CH3、氯-Cl、氟-F和叔丁基-tBu中任意一种。
优选的,N-三苯基亚胺吡啶钯配合物制备方法为:在氮气氛围下,将N- 三苯基亚胺吡啶配体和(COD)PdMeCl按摩尔比1:0.5-2混合并溶解在惰性溶剂中,室温下搅拌反应12-48h;搅拌结束后,在旋转蒸发器皿中采用减压蒸馏方式直至观察到开始出现固体产物;停止旋蒸,在剩余惰性溶剂和固体产物中加入10-50ml乙醚稀释,得到黄色沉淀物;过滤并真空干燥该黄色沉淀物,即得到所需的N-三苯基亚胺吡啶钯配合物。
反应过程为:
优选的,所述惰性溶剂为二氯甲烷或三氯甲烷。
本发明的目的之四在于提供上述N-三苯基亚胺吡啶镍配合物和上述N-三苯基亚胺吡啶钯配合物作为烯烃聚合反应的催化剂的应用。
优选的,所述应用为:N-三苯基亚胺吡啶镍配合物对乙烯、丙烯或α-烯烃中任意一种或多种进行催化聚合,得到低分子量(数均分子量Mn在1000- 2000g/mol)和具有甲基支和大量的长链支或支上支(最高比例达40%)微观结构的超支化(枝度高在69-100/1000C)聚烯烃。
优选的,所述应用为:N-三苯基亚胺吡啶钯配合物对乙烯、丙烯或α-烯烃中任意一种或多种进行催化聚合,得到低分子量(数均分子量Mn在260- 800g/mol),具有大量的长链支或支上支(高达87%)微观结构的超支化(枝度高在127-165/1000C)的乙烯齐聚物。
优选的,所述N-三苯基亚胺吡啶钯配合物对烯烃与丙烯酸酯类化合物进行催化共聚,获得高插入比(约为10mol%)的、低分子量(260~787g/mol) 的烯烃-丙烯酸酯类。
优选的,所述丙烯酸酯类化合物为丙烯酸甲酯。
本发明的有益效果在于:
1.本发明提供的N-三苯基亚胺吡啶配体为含2,6-二-(4-R-苯基)-4-甲基的亚胺吡啶配体,并基于其制备了N-三苯基亚胺吡啶Ni(II)、Pd(II)配合物,通过引入2,6-二-(4-R-苯基)-4-甲基苯胺,两个分子结构中的邻芳基都偏离了金属中心,不能对金属中心的轴向位置提供有效的屏蔽,从而导致聚合过程中快速的链转移或者链行走,进而获得低分子量的超支化无定型聚烯烃。
2.采用传统的催化方法很难制备出具有超支化结构的低分子量乙烯低聚物。本发明提供了一种简单高效合成一系列N-三苯基亚胺吡啶配体及相应的带有不同电子效应(H,Me,t-Bu,F,Cl)的远端共轭取代基的Ni(II)和Pd(II)配合物,这些 N-三苯基亚胺吡啶Ni(II)配合物和N-三苯基亚胺吡啶Pd(II)配合物作为烯烃齐聚或烯烃与丙烯酸酯类共聚反应中的催化剂,能够得到具有大量长链支或支上支结构组成的超支化、低分子量、高插入比的极性功能化聚烯烃或烯烃-丙烯酸酯类共聚物,在生产功能化聚烯烃上具有广阔的应用前景。
3.本发明提供的N-三苯基亚胺吡啶镍(II)配合物和钯(II)配合物可以作为烯烃聚合反应的催化剂,由于其供电子和大位阻效应,部分屏蔽了金属中心轴向结合位点,在与丙烯酸酯的结合中表现出了很高的效率,能有效地促进烯烃与丙烯酸酯类的共聚反应,得到高度支化的较高插入比的极性功能化烯烃-丙烯酸酯类共聚物。另外现有技术中对调节聚乙烯分支密度较难,本发明提供的N-三苯基亚胺吡啶钯(Ⅱ)配合物与现有的Pd(II)催化剂相比,可产生更高的支链聚乙烯和E-MA共聚物。
附图说明
图1A-E分别对应为N-三苯基亚胺吡啶配体L1-L5的核磁氢谱。
图2A-E分别对应为N-三苯基亚胺吡啶配体Ni1-Ni5的质谱。
图3A为N-三苯基亚胺吡啶钯配合物Pd1的核磁氢谱;图3B N-三苯基亚胺吡啶钯配合物Pd1的质谱。
图4A为N-三苯基亚胺吡啶钯配合物Pd2的核磁氢谱;图4B为N-三苯基亚胺吡啶钯配合物Pd2的质谱。
图5A为N-三苯基亚胺吡啶钯配合物Pd3的核磁氢谱;图5B为N-三苯基亚胺吡啶钯配合物Pd3的质谱。
图6A为N-三苯基亚胺吡啶钯配合物Pd4的核磁氢谱;图6B为N-三苯基亚胺吡啶钯配合物Pd4的质谱。
图7A为N-三苯基亚胺吡啶钯配合物Pd5的核磁氢谱;图7B为N-三苯基亚胺吡啶钯配合物Pd5的质谱。
上述核磁共振所用的氘代溶剂在使用前经过干燥和蒸馏,氢谱由JNM- ECZ600R光谱仪在室温下记录。
上述通过(ESI)LCMS-2010A来完成N-三苯基亚胺吡啶配体L1、L2、L3、 L4和L5的质谱分析,通过Auto flex Speed MALDI-TOF MS来完成N-三苯基亚胺吡啶镍配合物Ni1、Ni2、Ni3、Ni4和Ni5和N-三苯基亚胺吡啶钯配合物Pd1、 Pd2、Pd3、Pd4和Pd5的质谱分析。
具体实施方式
除非另有说明,本文中所使用的术语均具有本领域技术人员常规理解的含义。
下面结合实施例对本发明的技术方案做出更为具体的说明:
实施例1:
一种N-三苯基亚胺吡啶配体L1,其结构式如下所示:
S1.在圆底烧瓶中放入ZnCl2(0.34g,2.5mmol)、2-乙酰吡啶(20.0mmol) 和5mL冰醋酸形成悬浮液,加入2mmol的2,6-二-苯基-4-甲基苯胺,加热搅拌回流4h;
S2.S1中溶液冷却至室温,沉淀出亮黄色固体,过滤并分离该亮黄色固体,依次使用5mL乙酸洗涤三遍、5mL乙醚洗涤5遍,去除残留的乙酸后,在真空下干燥得到亮黄色提纯固体;
S3.将上述亮黄色提纯固体放入盛有30mL二氯甲烷的圆底烧瓶中,加入草酸钾(0.41g,2.2mmol)水溶液5mL,并快速搅拌1h;
S4.搅拌后溶液进行两相分离,20mL水洗有机溶剂层三遍,并用MgSO4干燥除去有机溶剂层水,再减压过滤;
S5.过滤后在真空去除溶剂,得到黄色粉末产品,在高真空下干燥,即得到目标产物N-三苯基亚胺吡啶L1。
本申请制备L1所得质量0.27g,产率75%。L1的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)δ8.49(d,J=4.4Hz,1H,Ar-H),7.98(d,J=7.9Hz, 1H,Ar-H),7.68(t,J=7.5Hz,1H,Ar-H),7.46(d,J=7.6Hz,4H,Ar-H),7.29(t,J=7.1 Hz,4H,Ar-H),7.26(s,1H,Ar-H),7.25(s,2H,Ar-H),7.21(t,J=7.3Hz,2H,Ar-H), 2.48(s,3H,CH3),1.89(s,3H,Ar-C(CH3)=N).13C NMR(151MHz,CDCl3)δ 167.21(C=N),156.29,148.27,144.17,140.48,136.26,133.44,131.94,130.48,129.37, 127.92,126.65,124.48,121.39,20.94(CH3),17.90(Ar-C(CH3)=N).
APCI-MS(m/z):calcd for C26H23N2:363.1856,Found,363.1842,[M+H]+.
实施例2:
一种N-三苯基亚胺吡啶配体L2,其结构式如下所示:
L2的制备方法同L1,不同在于将步骤S1中2,6-二-苯基-4-甲基苯胺替换为2,6-二-(4-甲基-苯基)-4-甲基苯胺。
本申请制备L2所得质量0.30g,产率78%。L2的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)δ8.49(d,J=4.5Hz,1H,Ar-H),8.02(d,J=8.0Hz, 1H,Ar-H),7.68(td,J=7.9,1.4Hz,1H,Ar-H),7.32(d,J=7.9Hz,4H,Ar-H),7.25– 7.23(m,1H,Ar-H),7.18(s,2H,Ar-H),7.06(d,J=7.9Hz,4H,Ar-H),2.43(s,3H,CH3), 2.29(s,6H,Ar-CH3),1.87(s,3H,Ar-C(CH3)=N).
APCI-MS(m/z):calcd for C28H27N2:391.2169,Found,391.2159,[M+H]+.
实施例3:
一种N-三苯基亚胺吡啶配体L3,其结构式如下所示:
L3的制备方法同L1,不同在于将步骤S1中2,6-二-苯基-4-甲基苯胺替换为2,6-二-(4-氟基-苯基)-4-甲基苯胺。
本申请制备L3所得质量0.32g,产率80%。L3的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)δ8.50(d,J=4.5Hz,1H,Ar-H),7.97(d,J=8.0Hz, 1H,Ar-H),7.72–7.63(m,1H,Ar-H),7.42–7.38(m,4H,Ar-H),7.27–7.25(m,1H,Ar- H),7.19(s,2H,Ar-H),6.99–6.94(m,4H,Ar-H),2.44(s,3H,CH3),1.88(s,3H,Ar- C(CH3)=N).13C NMR(151MHz,CDCl3)δ167.52(C=N),162.62,161.00,155.95, 148.45,144.23,136.38,136.31,136.30,133.64,130.99,130.93,130.88,130.47, 124.73,121.18,114.96,114.82,20.89(CH3),17.92(Ar-C(CH3)=N).19F NMR(565 MHz,CDCl3)δ-113.14–-117.42(m).
APCI-MS(m/z):calcd for C26H21F2N2:399.1667,Found,399.1650,[M+H]+.
实施例4:
一种N-三苯基亚胺吡啶配体L4,其结构式如下所示:
L4的制备过程同L1,不同在于将步骤S1中2,6-二-苯基-4-甲基苯胺替换为2,6-二-(4-氯基-苯基)-4-甲基苯胺。
本申请制备L4所得质量0.34g,产率78%。L4的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)δ8.50(d,J=4.4Hz,1H,Ar-H),7.98(d,J=7.9Hz, 1H,Ar-H),7.69(td,J=7.8,1.5Hz,1H,Ar-H),7.37(d,J=8.4Hz,4H,Ar-H),7.28–7.26(m,1H,Ar-H),7.23(d,J=8.5Hz,4H,Ar-H),7.18(s,2H,Ar-H),2.43(s,3H,CH3), 1.87(s,3H,Ar-C(CH3)=N).13C NMR(151MHz,CDCl3)δ167.61(C=N),155.79, 148.53,148.47,144.17,138.75,136.43,133.77,132.71,130.78,130.65,130.63, 128.22,128.18,124.85,124.80,121.16,20.89(CH3),17.87(Ar-C(CH3)=N).
APCI-MS(m/z):calcd for C26H21Cl2N2:431.1076,Found,431.1068,[M+H]+.
实施例5:
一种N-三苯基亚胺吡啶配体L5,其结构式如下所示:
L5的制备过程同L1,不同在于将步骤S1中2,6-二-苯基-4-甲基苯胺替换为2,6-二-(4-叔丁基-苯基)-4-甲基苯胺。
本申请制备L5所得质量0.33g,产率70%。L5的氢谱和质谱如下:
1H NMR NMR(600MHz,CDCl3)δ8.47(d,J=4.5Hz,1H,Ar-H),7.93(d,J= 8.0Hz,1H,Ar-H),7.67–7.64(m,1H,Ar-H),7.34(d,J=8.3Hz,4H,Ar-H),7.27(d,J =6.9Hz,4H,Ar-H),7.26–7.22(m,1H,Ar-H),7.20(s,2H,Ar-H),2.42(s,3H,CH3), 1.86(s,3H,Ar-C(CH3)=N),1.27(s,18H,C(CH3)3).
APCI-MS(m/z):calcd for C34H39N2:475.3108,Found,475.3093,[M+H]+.
实施例6
利用实施例1-5中制备的N-三苯基亚胺吡啶配体L1、L2、L3、L4和L5分别与镍化合物(DME)NiBr2反应,制备得到N-三苯基亚胺吡啶镍配合物Ni1、 Ni2、Ni3、Ni4和Ni5。
制备方法为:在氮气氛围下,将0.2mmolN-三苯基亚胺吡啶配体(L1、L2、 L3 L4和L5)和(DME)NiBr2(62mg,0.2mmol)溶解在装有5mL二氯甲烷的施莱克瓶中,在室温下搅拌10h,随着搅拌进行,溶液的颜色逐渐加深。搅拌结束后,旋转蒸发器中减压下蒸发,得到固体,并用5ml己烷洗涤四次,然后真空干燥,得到所需的N-三苯基亚胺吡啶镍配合物(Ni1、Ni2、Ni3、Ni4和Ni5)。
其中,Ni1的结构式为:
制备得到的Ni1质量为98mg,产率84%。Ni1的质谱如下:
MALDI-TOF MS(m/z):calcd for C26H22BrN2Ni:499.0320,Found:499.0328, [M-Br]+.Elemental analysis:calc.forC26H22Br2N2Ni:C,53.75;H,3.82;N,4.82. Found:C,53.84;H,3.79;N,4.87.
Ni2的结构式为:
制备得到的Ni2质量为111mg,产率91%。Ni2的质谱如下:
MALDI-TOF MS(m/z):calcd for C28H26BrN2Ni:527.0633,Found:527.0651, [M-Br]+.Anal.Calcd for C28H26BrN2Ni:C,55.22;H,4.30;N,4.60.Found:C,55.12;H, 4.35;N,4.69.
Ni3的结构式为:
制备得到的Ni3质量为110mg,产率89%。Ni3的质谱如下:
MALDI-TOFMS(m/z):calcdforC26H20BrF2N2Ni:535.0131,Found:535.0127,[M- Br]+.Elemental analysis:calc.for C26H20Br2F2N2Ni:C,50.62;H,3.27;N,4.54.Found: C,50.43;H,3.36;N,4.71.
Ni4的结构式为:
制备得到的Ni4质量为116mg,产率94%。Ni4的质谱如下:
MALDI-TOFMS(m/z):calcd for C26H20BrCl2N2Ni:566.9540,Found:566.9538, [M-Br]+.Elemental analysis:calc.for C26H20Br2Cl2N2Ni:C,48.05;H,3.10;N,4.31. Found:C,48.25;H,3.14;N,4.51.
Ni5的结构式为:
制备得到的Ni5质量为121mg,产率87%。Ni5的质谱如下:
ESI-MS(m/z):calcd for calcd for C34H38BrN2Ni:611.1572,Found:611.1581,[M- Br]+.Elemental analysis:calc.forC34H38Br2N2Ni:C,58.91;H,5.53;N,4.04.Found:C,58.85;H,5.64;N,4.11.
实施例7
利用实施例1-5中制备的N-三苯基亚胺吡啶配体L1、L2、L3、L4和L5分别与钯化合物Pd(COD)MeCl反应,制备得到N-三苯基亚胺吡啶钯配合物Pd1、 Pd2、Pd3、Pd4和Pd5。
制备方法为:在氮气氛围下,将0.5mmolN-三苯基亚胺吡啶配体(L1、L2、 L3、L4和L5)和Pd(COD)MeCl(133mg,0.5mmol)溶解在10mL二氯甲烷中,在室温下搅拌24h,随着搅拌进行,溶液的颜色逐渐加深。搅拌结束后,在旋转蒸发皿中减压蒸馏的直到看到少量固体产物。将混合物用20ml乙醚稀释,获得黄色沉淀,过滤收集黄色固体,并真空干燥,获得样品。
其中,Pd1的结构式为:
本实施例制备的Pd1质量为236mg,产率91%。Pd1的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)a-isomer:b-isomer=10:1δ9.11,8.97(d,J=4.4Hz, 1H,Ar-H),7.83(td,J=7.9,1.5Hz,1H,Ar-H),7.79,7.57(d,J=7.5Hz,4H,Ar-H), 7.53(d,J=7.9Hz,1H,Ar-H),7.49(dd,J=7.3,5.6Hz,1H,Ar-H),7.76,7.30(t,J= 7.7Hz,4H,Ar-H),7.36,7.23–7.20(m,4H,Ar-H),2.46(s,3H,CH3),2.02(s,3H,Ar- C(CH3)=N),0.66(s,3H,Pd-CH3).13C NMR(151MHz,CDCl3)δ173.77(C=N), 152.20,149.33,139.73,138.75,138.34,137.20,134.30,131.15,129.38,128.40, 128.14,127.59,124.55,21.04(CH3),19.45(Ar-C(CH3)=N),0.61(Pd-CH3).
MALDI-TOFMS(m/z):calcd for C26H22N2Pd:468.0818,Found:468.0791,[M- Me-Cl]+;calcd for C27H25N2Pd:483.1053,Found:483.1054,[M-Cl]+;calcd for C26H22ClN2Pd:503.0506,Found:503.0496,[M-Me]+.Elemental analysis:calc. forC27H25ClN2Pd:C,62.44;H,4.85;N,5.39.Found:C,62.35;H,4.67;N,5.41.
其中,Pd2的结构式为:
本实施例制备的Pd2质量为253mg,产率92%。Pd2的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)a-isomer:b-isomer=10:1δ9.19,9.02(d,J=4.9 Hz,1H,Ar-H),7.95,7.85(t,J=7.8Hz,1H,Ar-H),7.55(d,J=7.8Hz,1H,Ar-H), 7.52(dd,J=7.3,5.4Hz,1H,Ar-H),7.68,7.44(t,J=7.6Hz,4H,Ar-H),7.19(s,2H, Ar-H),7.15,7.09(d,J=7.8Hz,4H,Ar-H),2.44(s,3H,CH3),2.27(s,6H,Ar-CH3), 2.02(s,3H,Ar-C(CH3)=N),0.65(s,3H,Pd-CH3).13C NMR(151MHz,CDCl3)δ 173.57(C=N),152.31,149.38,139.74,138.22,137.18,137.01,135.88,134.24,131.01, 129.22,129.11,128.06,124.48,21.24(Ar-CH3),21.03(CH3),19.39(Ar-C(CH3)=N), 0.64(Pd-CH3).
ESI-MS(m/z):calcd for C28H26N2Pd:496.1131,Found:496.1134,[M-Me- Cl]+;calcd for C29H29N2Pd:511.1366,Found:511.1380,[M-Cl]+;calcd for C28H26N2ClPd:531.0819,Found:531.0808,[M-Me]+.Anal.Calcd forC29H29ClN2Pd: C,63.63;H,5.34;N,5.12.Found:C,63.58;H,5.47;N,5.27.
Pd3的结构式为:
本实施例制备的Pd3质量为248mg,产率89%。Pd3的氢谱和质谱如下:
1H NMR a-isomer:b-isomer=10:11H NMR(600MHz,CDCl3)δ9.03,8.52(d, J=5.2Hz,1H,Ar-H),7.89(td,J=7.7,1.3Hz,1H,Ar-H),7.80–7.76(m,1H,Ar-H), 7.59(d,J=7.3Hz,1H,Ar-H),7.56(dd,J=7.7,4.5Hz,4H,Ar-H),7.20,7.12(s,2H, Ar-H),7.00(t,J=8.7Hz,4H,Ar-H),2.45,2.40(s,3H,CH3),2.00,1.88(s,3H,Ar- C(CH3)=N),0.97,0.64(s,3H,Pd-CH3).13C NMR(151MHz,CDCl3)δ173.86(C=N), 163.00,161.36,152.00,149.52,139.83,138.49,137.43,134.54,133.34,131.27, 131.08,131.03,128.43,124.68,115.57,115.42,21.00(CH3),19.37(Ar-C(CH3)=N), 0.67(Pd-CH3).19F NMR(565MHz,CDCl3)δ-114.00(s),-115.24(s).
ESI-MS(m/z):calcd for C26H20F2N2Pd:504.0629,Found:504.0635,[M-Me-Cl]+;calcd for C27H23F2N2Pd:519.0864,Found:519.0898,[M-Cl]+;calcd for C26H20ClF2N2Pd:539.0318,Found:539.0312,[M-Me]+.Anal.Calcd for C27H23ClF2N2Pd:C,58.39;H,4.17;N,5.04.Found:C,58.31;H,4.23;N,5.21.
Pd4的结构式为:
本实施例制备的Pd4质量为266mg,产率90%。Pd4的氢谱和质谱如下:
1H NMR a-isomer:b-isomer=10:11H NMR(600MHz,CDCl3)δ9.20,9.04(d, J=4.7Hz,1H,Ar-H),8.54,7.89(d,J=5.2Hz,1H,Ar-H),7.76(dd,J=21.2,8.3Hz, 1H,Ar-H),7.59(t,J=6.5Hz,1H,Ar-H),7.55(d,J=8.5Hz,4H,Ar-H),7.28(d,J= 8.8Hz,4H,Ar-H),7.20(s,2H,Ar-H),2.45,2.40(s,3H,CH3),2.00,1.87(s,3H,Ar- C(CH3)=N),0.99,0.64(s,3H,Pd-CH3).13C NMR(151MHz,CDCl3)δ173.98(C=N), 151.90,149.58,139.68,138.51,137.56,137.00,133.80,133.18,131.39,131.24, 130.66,128.74,128.53,128.23,124.82,20.99(CH3),19.37(Ar-C(CH3)=N),0.64(Pd- CH3).
MALDI-TOFMS(m/z):calcd for C26H20Cl2N2Pd:536.0038,Found:536.0032, [M-Me-Cl]+;calcd for C27H23Cl2N2Pd:553.0277,Found:553.0309,[M-Cl]+;calcd forC26H20Cl3N2Pd:570.9727,Found:570.9746,[M-Me]+.Elemental analysis:calc.forC27H23Cl3N2Pd:C,55.13;H,3.94;N,4.76.Found:C,55.24;H,4.12;N,4.87.
Pd5的结构式为:
本实施例制备的Pd5质量为0.275g,产率87%。Pd5的氢谱和质谱如下:
1H NMR(600MHz,CDCl3)δ8.94(d,J=4.6Hz,1H,Ar-H),7.81(td,J=7.8, 1.4Hz,1H,Ar-H),7.58–7.54(m,4H,Ar-H),7.53(d,J=7.6Hz,1H,Ar-H),7.45(dd, J=7.1,5.6Hz,1H,Ar-H),7.33–7.31(m,4H,Ar-H),7.20(s,2H,Ar-H),2.43(s,3H, CH3),2.01(s,3H,Ar-C(CH3)=N),1.24(s,18H,C(CH3)3),0.68(s,3H,Pd-CH3).13C NMR(151MHz,CDCl3)δ173.71(C=N),152.30,150.33,149.22,139.88,138.22, 136.95,135.86,134.09,131.11,129.10,128.06,125.27,124.42,34.58(C(CH3)3), 31.33(C(CH3)3),21.01(CH3),19.46(Ar-C(CH3)=N),0.56(Pd-CH3).
ESI-MS(m/z):calcd for C34H38N2Pd:580.2070,Found:580.2058,[M-Me-Cl]+;calcd for C35H41N2Pd:595.2305,Found:595.2377,[M-Cl]+;calcd for C34H38N2ClPd:615.1758,Found:615.1751,[M-Me]+.Anal.Calcd for C35H41N2ClPd:C,66.56;H,6.54; N,4.44.Found:C,66.45;H,6.38;N,4.29.
实施例8
利用实施例6制备的N-三苯基亚胺吡啶镍配合物Ni1、Ni2、Ni3、Ni4和 Ni5为催化剂进行乙烯均聚,方法为:
首先在真空90℃下干燥一台连接高压气体管路的350mL不锈钢压力反应器,干燥时间至少为1h;然后将反应器调整到所需的聚合温度(本实验实施温度为30℃、50℃和70℃)。在氮气气氛下向反应器中加入20mL甲苯以及所需量的氯化二乙基铝Et2AlCl,然后通过注射器将含所需N-三苯基亚胺吡啶镍催化剂的1mL二氯甲烷溶液注入聚合体系中,本实施例中催化剂加入量为1μmol。快速搅拌后,反应器加压并保持在6atm的乙烯状态。在所需的时间后,将压力反应器放空,将聚合物在真空下干燥过夜。
上述催化反应中,Ni1、Ni2、Ni3、Ni4和Ni5分别在30℃、50℃和70℃条件下进行1次,对各组的催化聚合物产物进行测试,测得各项数据如下表1 所示。表中Ni0项为对照组数据,对照数据使用含二亚胺配合体Ni催化剂,记为Ni0,其结构式表示如下:
对照数据在50℃、70℃下聚合,其他反应条件同试验组,在最优化聚合条件下进行。
聚合物的分子量和分子量分布均通过凝胶渗透色谱法(GPC),以四氢呋喃溶剂在40℃的条件下测定,并使用聚苯乙烯为标准进行校准。
表1 Ni1、Ni2、Ni3、Ni4和Ni5催化聚合产物比较
本申请制备的N-三苯基亚胺吡啶镍配合物显示出非常高的乙烯齐聚活性(Act.b)5.5-7.8*106g·mol-1·h-1;用Ni1-Ni5做催化剂制备的乙烯低聚物分子量低 (约1-2kg/mol),分枝度高(69-100/1000C),呈蜡状或油状。从表1中可以看出,本申请制备的N-三苯基亚胺吡啶镍配合物Ni1、Ni2、Ni3、Ni4和Ni5的催化活性Act.b和分枝密度均随温度升高而先增后降,聚合温度对催化效果具有影响;随温度的升高,聚乙烯的分子量Mn c降低,说明生成了低分子量的高支链聚乙烯。对照组生成的聚乙烯对比Ni1-Ni5,分子量更小,活性更低,其得到的聚乙烯分枝密度Be差异较小,说明受聚合温度影响较小,这主要是因为在N-三苯基亚胺吡啶镍配合物体系中,温度的升高,链的行走和转移速度大于链的生长速度。此外,对照组催化剂生成相当支化度(80/1000C)低分支密度的聚乙烯,所获得的聚乙烯分子量分布范围PDI=Mw/Mn d分布在1.5-1.6之间,而Ni1、Ni2、 Ni3、Ni4和Ni5生成的高支化聚乙烯,其分子量分布范围PDI仅在1.32-1.46之间,同时催化剂对乙烯齐聚具有良好的热稳定性,表明本申请的N-三苯基亚胺吡啶镍配合物体系可以显著地影响聚合物的微观结构。
实施例9
利用实施例5制备的N-三苯基亚胺吡啶钯配合物Pd1-Pd5作为催化剂进行乙烯均聚,方法为:
首先在真空90℃下干燥一台连接高压气体管路的350mL不锈钢压力反应器,干燥时间至少为1h;然后将反应器调整到所需的聚合温度(本实验实施温度为30℃、50℃和70℃)。在氮气气氛下向反应器中加入20mL甲苯以及所需量的Et2AlCl,然后通过注射器将含所需N-三苯基亚胺吡啶镍催化剂的1mL二氯甲烷溶液注入聚合体系中,本实施例中催化剂加入量为1μmol。快速搅拌后,反应器加压并保持在6atm的乙烯状态。在所需的时间后,将压力反应器放空,将聚合物在真空下干燥过夜。
上述催化反应中,Pd1、Pd2、Pd3、Pd4和Pd5分别在30℃和50℃条件下进行1次,则试验分别得到Pd1、Pd2、Pd3、Pd4和Pd5催化剂的10份催化聚合物产物,测得聚聚合物产物的各项数据如下表2所示。表中Pd0项为对照组数据,Pd0结构式表示如下:
对照数据在30℃、50℃下聚合,其他反应条件同试验组,在最优化聚合条件下进行。
表2 Pd1、Pd2、Pd3、Pd4和Pd5催化聚合产物比较
从表2中可以看出,Pd1-Pd5作为催化剂进行乙烯均聚,得到的乙烯低聚物的活性和支化度随温度的升高而显著增加,分子量则稍有降低。这一趋势突出表明,高温有利于链转移和链行走反应,同时也增加了乙烯插入的速率。从表 2中可以看出,具有吸电子取代基的催化剂Pd3和Pd4生成了分子量较低、支化度较低(最高为146/1000C和148/1000C)的乙烯低聚物。具有供电子和体积较大的tBu基团的催化剂Pd5在50℃下生成了分子量大、支化度很高 (154/1000C)的乙烯低聚物。因此,以本申请制备的Pd1-Pd5作为催化剂,通过调整聚合温度和精确调控催化剂中杂化苯胺基团的电子效应和空间位阻,可以获得高支化程度和高插入比的烯烃共聚合物。
对照组生成的聚乙烯,在同样的聚合条件下,除了活性较好之外,所获得的低分子量烯烃聚合物分子量更小,支化程度在30℃下为106/1000C,50℃下为124/1000C,远低于使用本申请制备的Ni1-Ni5。
实施例10
利用实施例4制备的N-三苯基亚胺吡啶钯配合物Pd1-Pd5作为催化剂将丙烯酸甲酯与乙烯共聚,试验方法为:
首先在真空90℃下干燥一台连接高压气体管路的350mL不锈钢压力反应器,干燥时间至少为1h;然后将反应器调整到所需的聚合温度(本实验实施温度为30℃),在氮气气氛下向反应器中加入18mL的二氯甲烷与极性单体的混合溶液和所需量的NaBArF(本实施例中的NaBArF加入量为0.04mmol,极性单体为1mol/L),然后通过注射器将2mL含所需N-三苯基亚胺吡啶钯配合物的二氯甲烷溶液注入聚合体系(本实施例中催化剂加入量为0.02mmol)中。在快速搅拌后,共聚反应12h后,将压力反应器放空,然后将聚合物在真空下干燥过夜。
上述催化反应中,Pd1-Pd5分别在30℃条件下进行,则试验分别得到Pd1、 Pd2、Pd3、Pd4和Pd5五份催化剂的5份催化聚合物产物,测得聚合物产物的各项数据如下表2所示。表中Pd0项为对照组数据。
表3 Pd1、Pd2、Pd3、Pd4和Pd5催化聚合产物比较
插入比是极性丙烯酸酯类单体占所有单体的比值,与功能化聚乙烯关系密切。由表3可以看出,在乙烯-MA共聚反应中,Pd1、Pd2、Pd3、Pd4和Pd5的产物中,具有吸电子取代基的催化剂Pd3-Pd4,共聚活性Act.b高,但是E-MA 齐共聚物分子量和掺入比均降低。具有供电子和大空间位阻的催化剂Pd5共聚活性适中,得到分子量最大的高支化度E-MA低分子量共聚物,其掺入比也最高(高达8.92mol%)。从表3可以看出,亚胺吡啶Pd(II)催化剂可以高效地催化烯烃(乙烯或丙烯)和极性单体共聚反应,制备出一系列高插入比(2.6-8.9mol%)的超高度支化(144-151)的极性功能化的低分子量E-MA齐共聚物。结果表明,通过精确调控催化剂中杂化苯胺基团的电子效应和空间位阻,可以获得高支化程度和高插入比的烯烃共聚合物。进一步研究发现,N-三苯基亚胺吡啶钯配合物有利于长链和枝上枝的拓扑结构产生,所有长枝结构的比例高达87%,催化产生的共聚物的甲基支很少(13-16%)。这表明钯化合物比相应的镍化合物能进行更深入的链异构化,并给出更拓扑的分子结构。
而对照组中虽然活性较高,但产物插入比和支化度相对较低。在分子量相当的情况下,分支化度仅为120/1000C,极性基团的插入比仅1.73mol%左右。说明本发明提供的N-三苯基亚胺吡啶钯配合物作为催化剂具有很好地催化高插入比和高支化度的烯烃共聚反应的能力。进一步研究发现,齐聚温度不仅影响乙烯齐聚物的总分枝量,而且影响齐聚物的分枝分布。低聚温度越高,乙烯低聚物的长链分枝比例越高,尤其是分枝上的基团,说明该体系的过分枝可以由温度调节。
以上实施方式仅用以说明本发明的技术方案,而并非对本发明的限制;尽管参照前述实施方式对本发明进行了详细的说明,本领域的普通技术人员应当理解:凡在本发明创造的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明创造的保护范围之内。
Claims (10)
2.如权利要求1所述的N-三苯基亚胺吡啶配体的制备方法,其特征在于,步骤如下:
S1.在圆底烧瓶中放入0.5-4N的ZnCl2、10-50N的2-乙酰吡啶和3-10mL冰醋酸的悬浮液,加入0.8-3N的2,6-二-(4-R-苯基)-4-甲基苯胺同类物,加热搅拌回流1-6h,冷却至室温;N为当量值;
S2.S1中溶液冷却至室温,沉淀出亮黄色固体,过滤并分离所述亮黄色固体,依次使用乙酸和乙醚洗涤后,在真空下干燥得到橘红色提纯固体;
S3.将所述橘红色提纯固体放入盛有10-60mL二氯甲烷的圆底烧瓶中,加入1-6N草酸钾水溶液3-20mL,并以1000-2000r/min速度搅拌30-80min;
S4.搅拌后溶液进行两相分离,水洗有机溶剂层,并用MgSO4干燥除去有机溶剂层水,再减压过滤;
S5.过滤后在真空干燥箱中去除溶剂,得到产物即为所需的N-三苯基亚胺吡啶配体。
3.如权利要求2所述的N-三苯基亚胺吡啶配体的制备方法,其特征在于,所述2,6-二-(4-R-苯基)-4-甲基苯胺同类物的制备方法,具体步骤为:
S11.氮气气氛下,将10-30N的4-R-苯基硼酸、5-20N的2,6-二溴-4-甲基-苯胺、1-2N的四(三苯基膦)钯Pd(PPh3)4和30-100N的K2CO3的混合物加入四氢呋喃与水的混合物液中,再将混合物液加热至65-80℃,搅拌18-36h;四氢呋喃与水以4:1~6:1体积比混合;
S12.将反应后的混合物液转移到旋转蒸发器中,去除溶剂,并用二氯甲烷提取残渣,继续转移到分液漏斗,加入水,震荡后静置分离出下层有机相,并用MgSO4干燥所述有机相;
S13过滤除去MgSO4固体,将有机相转移到旋转蒸发器中浓缩,浓缩液通过硅胶柱层析分离,分离得到的第二个组分即为2,6-二-(4-R-苯基)-4-甲基苯胺同类物。
5.如权利要求4所述的N-三苯基亚胺吡啶镍配合物的制备方法,其特征在于,该制备方法为:在氮气氛围下,将N-三苯基亚胺吡啶配体和(DME)NiBr2按摩尔比1:(0.5-2)混合并溶解在二氯甲烷或三氯甲烷中,室温下搅拌反应6-24h;搅拌结束后,在旋转蒸发器皿中采用减压蒸馏方式得到固体产物,并将所述固体产物用乙烷洗涤,真空干燥得到所需的N-三苯基亚胺吡啶镍配合物。
7.如权利要求6所述的N-三苯基亚胺吡啶钯配合物的制备方法,其特征在于,该制备方法为:在氮气氛围下,将N-三苯基亚胺吡啶配体和(COD)PdMeCl按摩尔比1:(0.5-2)混合并溶解在二氯甲烷或三氯甲烷中,室温下搅拌反应12-48h;搅拌结束后,在旋转蒸发器皿中采用减压蒸馏方式直至观察到开始出现固体产物;停止旋蒸,在剩余惰性溶剂和固体产物中加入10-50ml乙醚稀释,得到黄色沉淀物;过滤并真空干燥该黄色沉淀物,即得到所需的N-三苯基亚胺吡啶钯配合物。
8.一种权利要求4所述的N-三苯基亚胺吡啶镍配合物或权利要求6所述的N-三苯基亚胺吡啶钯配合物作为烯烃聚合反应的催化剂的应用。
9.如权利要求8所述的应用,其特征在于,所述应用具体为:N-三苯基亚胺吡啶镍配合物对乙烯、丙烯或α-烯烃中的任意一种或多种进行催化聚合,得到分子量在1000-2000g/mol,枝化度在69-100/1000C的聚烯烃。
10.如权利要求8所述的应用,其特征在于,所述应用具体为:N-三苯基亚胺吡啶钯配合物对乙烯、丙烯或α-烯烃中任意一种或多种进行催化聚合,得到分子量在260-800g/mol,枝化度在127-165/1000C的聚烯烃;
或所述N-三苯基亚胺吡啶钯配合物对烯烃与丙烯酸酯类化合物进行催化共聚,得到分子量为260-787g/mol,且插入比大于10mol%的烯烃-丙烯酸酯类共聚物;所述丙烯酸酯类化合物为丙烯酸甲酯。
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