CN107899614B - Binuclear xanthene bridged amido-nickel pyridine catalyst and preparation method and application thereof - Google Patents
Binuclear xanthene bridged amido-nickel pyridine catalyst and preparation method and application thereof Download PDFInfo
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- CN107899614B CN107899614B CN201711155478.1A CN201711155478A CN107899614B CN 107899614 B CN107899614 B CN 107899614B CN 201711155478 A CN201711155478 A CN 201711155478A CN 107899614 B CN107899614 B CN 107899614B
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- xanthene
- catalyst
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- nickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 title claims description 14
- -1 polyethylene Polymers 0.000 claims abstract description 25
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000005977 Ethylene Substances 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 11
- 229920000573 polyethylene Polymers 0.000 claims abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 230000000994 depressogenic effect Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000006384 oligomerization reaction Methods 0.000 claims description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 2
- 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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007872 degassing Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 abstract description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 abstract 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 239000002283 diesel fuel Substances 0.000 description 14
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000881 depressing effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- KZLCCMBSJDXNDG-UHFFFAOYSA-N azepan-1-yl(phenyl)methanone Chemical compound C=1C=CC=CC=1C(=O)N1CCCCCC1 KZLCCMBSJDXNDG-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- SSDIIKNSUCERSG-UHFFFAOYSA-N nickel;pyridine Chemical compound [Ni].C1=CC=NC=C1 SSDIIKNSUCERSG-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- AZOQYOYGOBQIIF-UHFFFAOYSA-N 4-bromo-1,2-dimethylcyclohexa-2,4-dien-1-amine Chemical compound CC1(N)CC=C(C=C1C)Br AZOQYOYGOBQIIF-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- YZFHHCGWJHVJRU-UHFFFAOYSA-N OBOBO.C1=CC=C2CC3=CC=CC=C3OC2=C1 Chemical compound OBOBO.C1=CC=C2CC3=CC=CC=C3OC2=C1 YZFHHCGWJHVJRU-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- QXDRRUNECCKDOL-UHFFFAOYSA-N nickel;pyridin-2-amine Chemical compound [Ni].NC1=CC=CC=N1 QXDRRUNECCKDOL-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing 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
- 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
-
- 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
-
- 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
-
- 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
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/16—Hydrocarbons
- C10L1/1625—Hydrocarbons macromolecular compounds
- C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
-
- 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
-
- 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
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a novel xanthene bridging amino-pyridine binuclear nickel catalyst and a preparation method thereof, and the catalyst is used for catalyzing ethylene polymerization to prepare polyethylene with lower polymerization degree and high branching degree.
Description
Technical Field
The invention belongs to the field of catalysis, and particularly relates to a binuclear xanthene bridged amido-nickel pyridine catalyst, and a preparation method and application thereof.
Background
The main reason why diesel fuel loses fluidity at low temperature is that wax in diesel fuel is crystallized out to form wax crystals. The wax crystals grow rapidly and bond into a net skeleton structure to wrap the diesel oil inside, so that the diesel oil loses fluidity. When the pour point depressant is added in a proper amount, although the precipitation of the wax cannot be prevented, the size and the shape of the wax can be changed to weaken the capability of wax crystals to form a network structure, so that the flow property of the diesel oil is improved.
The diesel pour point depressant developed at home at present is few in variety, and the Von beautiful and the like (Von beautiful, Zhangqing, Wang Fang, etc.. the performance of the AVS type diesel pour point depressant [ J ]. oilfield chemistry, 2013,30(4):586 ion 589,593) adopts a free radical polymerization method to synthesize 4 kinds of alkyl acrylate-vinyl acetate-styrene terpolymers with different alkyl chain lengths, and the pour point depressing and filtration reducing effect of the copolymer on diesel oil is determined to find that the AVS-16 pour point depressing effect is better, the diesel oil pour point can be reduced by 12 ℃, but the filtration reducing effect is poorer; the AVS-18 has better filtration reducing effect, can reduce the cold filter plugging point of diesel by 4 ℃, and has better pour point depressing effect.
Development of Wangjingjing (Wangjingjing, Decanting Happy, Tanshu. P (DBF-VA) type modifier for improving low-temp. flowability of diesel oil [ J)]Fine petrochemical 2006,23(6): 22-24) Synthesis of fumaric acid double-chain Mixed ester-vinyl acetate binary copolymer by radical polymerization, enabling Tuha-10#、0#The cold filter plugging point of the diesel oil is respectively reduced by 10 ℃ and 7 ℃; make the Dushan mountain 0#The cold filter plugging point of the diesel oil is reduced by 12 ℃; clarityl 0#The cold filter plugging point of the diesel oil is reduced by 8 ℃.
The pour point depressant is mostly an ester polymer or a copolymer of ester and olefin, and has higher reaction temperature and higher production cost.
Disclosure of Invention
The invention provides a binuclear xanthene bridged amido-nickel pyridine catalyst which has high catalytic activity and mild polymerization reaction conditions, can catalyze ethylene oligomerization, can prepare ethylene oligomer with high branching degree, can be directly used as an oil pour point depressant, takes ethylene as a raw material, and has low production cost.
The binuclear xanthene bridged amido-nickel pyridine catalyst provided by the invention has a structure shown in the following formula (I):
wherein R is independently methyl or isopropyl.
The preparation method of the catalyst comprises the following steps:
(1) mixing boric acid compound A and aniline compound B (excess) in a molar ratio of 3-4:10 in an organic solvent, adding Pd (dba)2(the addition amount is 20 percent (w) of the boric acid compound A)) and triphenylphosphine (the addition amount is 10 percent (w) of the boric acid compound A)) are stirred and reacted for 12-24h at room temperature to formDiamine compound C:
wherein R is independently methyl or isopropyl.
(2) The diamine compound C and the aldehyde compound D are heated and refluxed in an organic solvent for 12-24h according to a molar ratio of 1:6-7 under the catalysis of organic acid to form a ligand E:
wherein R is independently methyl or isopropyl.
(3) And (3) heating and refluxing the ligand E and trimethylaluminum in an organic solvent for 5-10h in a molar ratio of 1:6 under the catalysis of organic acid to form a ligand F:
wherein R is independently methyl or isopropyl.
(4) Ligands F and (DME) NiBr at room temperature2The compounds are reacted in a solvent according to a molar ratio of 1:2 to obtain the catalyst with the structure shown in the formula (I).
Wherein R is independently methyl or isopropyl.
The organic acid in the step (2) and the step (3) is one of formic acid, acetic acid, p-toluenesulfonic acid or camphorsulfonic acid; and (3) in the step (1), the step (2), the step (3) and the step (4), the organic solvent is one or more of toluene, xylene, chlorobenzene, tetrahydrofuran and dichloromethane.
The preparation method of the catalyst used for catalyzing ethylene to prepare polyethylene with low polymerization degree and high branching degree comprises the following steps: adding catalyst promoter MAO and aromatic solvent into thick-wall pressure-resistant glass container under anhydrous and oxygen-free conditionsAnd (4) stirring. Connecting a pressure-resistant bottle with an ethylene pipeline, degassing the solution, heating to a required temperature, introducing ethylene gas, and dissolving in CH2Cl2The nickel complex catalyst of formula (I) is injected into a polymerization system and reacts under rapid stirring. After the reaction is finished, the pressure is released, and the reaction is stopped in acidified methanol to prepare the polyethylene.
Wherein the reaction temperature is 0-80 ℃; the ethylene pressure is 1-5 atm; the reaction time is 0.5-2 h.
The high-branching-degree polyethylene prepared by the catalysis of the binuclear xanthene bridging amino-pyridine nickel catalyst is used as a diesel pour point depressant, the molecular weight of the polyethylene is 1000-4000, and the branching degree is more than 80.
Has the advantages that: the catalyst prepared by the invention has high catalytic activity and mild polymerization reaction conditions, can catalyze ethylene oligomerization, and can prepare ethylene oligomer with high branching degree; the prepared oligomer can be used as an oil pour point depressant, ethylene is used as a raw material to produce the pour point depressant, and the cost is lower compared with the current ester polymer or copolymer pour point depressant of esters and olefin.
Detailed Description
The following examples illustrate the details of the invention and show the synthesis of ligands and complexes and the method of ethylene polymerization. The synthesis and polymerization processes of the complex are carried out under anhydrous and oxygen-free conditions, all sensitive substances are stored in a glove box, and all solvents are strictly dried to remove water. Ethylene gas is purified by a water removal oxygen removal column. All raw materials were purchased and used as received if not specifically stated.
The apparatus used was characterized as follows:
the nuclear magnetism detection is carried out by a Bruker 400MHz nuclear magnetism instrument. Elemental analysis (Vario EL cube). Molecular weight and molecular weight distribution were determined by high temperature GPC. Mass spectra were determined using Thermo LTQ Orbitrap XL (ESI +) or P-SIMS-Gly of Bruker Daltonics Inc (EI +).
Example 1:
9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-diisopropyl) aniline-2-ethyl ] pyridine is synthesized by the following reaction formula.
Taking xanthene diboronic acid (1.0g,3.4mmol), 1, 6-diisopropyl p-bromophenylamine (2.6g, 10.0mmol), sodium carbonate (1.0g,9.4mmol), Pd (dba)2(0.2g,0.35mmol), triphenylphosphine (0.1g,0.4mmol), H2O (4mL), ethanol (7mL) and toluene (24mL) were mixed and stirred at room temperature overnight, after the reaction was stopped, extracted with ethyl acetate, washed with sodium chloride, dried over magnesium sulfate, the solvent was dried, recrystallized by adding 10mL methanol, filtered and dried to give 9, 9-dimethyl-9-xanthene-4, 4' -bis (2, 6-diisopropyl) aniline (diamine compound C) as an off-white solid (1.0g, 54%).
After 9, 9-dimethyl-9-xanthene-4, 4' -bis (2, 6-diisopropyl) aniline (1.0g,1.79mmol), 2-pyridinecarboxaldehyde (1.30g,12.1mmol) and 0.05 equivalent of p-toluenesulfonic acid were dissolved in toluene (30mL), the mixture was refluxed for 24h, during which the degree of reaction was monitored by spotting plates. After the reaction was completed, the solvent was spin-dried, 20ml of methanol was added to conduct recrystallization, the mixture was a yellow solid at-20 ℃, filtered, and dried in vacuo to give 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-diisopropyl) benzimine ] pyridine in 90% yield (1.21 g).
Taking 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-diisopropyl) benzimine]Pyridine (1.21g,2mmol), trimethylaluminum (12mmol) and 0.1 equivalent of p-toluenesulfonic acid were dissolved in toluene (25 mL). In N2And (3) refluxing for 5h under the protection of atmosphere, and adding 1N ice NaOH solution after the reaction is stopped. The organic layer was washed twice with saturated NaCl solution, Na2SO4Drying, spin-drying solvent, adding a large amount of n-hexane, filtering, repeatedly washing the obtained white solid with n-hexane for 3 times, and vacuum drying to obtain 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-diisopropyl) aniline-2-ethyl]Pyridine, 89% (1.12 g). 1H NMR (500MHz, CDCl3, ppm): δ 8.60(ddd, J ═ 5.0,1.9,1.0Hz,2H, pydine-H),7.52(dtd, J ═ 13.9,7.6,1.8Hz,2H, pydine-H),7.39(dd, J ═ 7.5,2.0Hz,2H, pydine-H), 7.10-7.17 (m,10H, pydine-H, aryl-H),7.04(ddt, J ═ 7.7,2.2,1.1Hz,2H, aryl-H),4.11(dd, J ═ 8.6,4.8Hz,2H, CHCH3),3.94(s,2H, NH), 3.03H, 3.03 ═ ch3(m,4H,CH(CH3)2),1.76(s,6H,xanthene-CH3),1.44(m,6H,CHCH3),0.95(d,J＝6.7Hz,12H,CH(CH3)2),0.77(d,J＝6.8Hz,12H,CH(CH3)2)；13C{1H}NMR(125MHz,CDCl3,ppm):δ163.6,149.3,146.9,141.2,141.0,136.2,132.7,130.7,130.4,130.1,124.8,124.6,122.7,121.9,121.7,60.6(CHCH3),34.1(CHCH3),33.9(C(CH3)2),33.7(C(CH3)2),27.5(CH(CH3)2),24.2(CH(CH3)2),24.1(CH(CH3)2),22.4(CH(CH3)2)；HRMS(m/z):calcd for C53H63N4O:771.5002；found:771.4367[M+H]+。
Example 2
9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-dimethyl) aniline-2-ethyl ] pyridine is synthesized by the following reaction formula.
The procedure was as above, and 1, 6-dimethyl-p-bromoaniline (2.0g,10mmol) was added to give 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-dimethyl) aniline-2-ethyl ] pyridine, 84% (1.01 g). 1H NMR (500MHz, CDCl3, ppm): delta 8.44(m,2H, pydine-H),7.33(m, pydine-H),7.19(d, J ═ 7.4Hz,2H, pydine-H),7.01(d, J ═ 8.0Hz,4H, pydine-H, aryl-H),6.9(m,4H, aryl-H),6.80(s,4H, aryl-H),4.31(m,4H, CHCH3),3.94(s,2H, NH),1.86(s,12H, aryl-CH3),1.53(m,6H, xanthene-CH3),1.36(m,6H, CHCH 3); 13C {1H } NMR (125MHz, CDCl3, ppm): delta 164.2,149.2,147.5,143.9,136.2,130.4,130.2,130.0,128.8,128.4,124.2,122.7,121.9,121.3,57.8(CHCH3),34.4(C (CH3)2),32.3(C (CH3)2),23.1(CHCH3),18.8(aryl-CH 3); HRMS (m/z) calcd for C45H47N4O: 659.3750; found 659.4578[ M + H ] +.
Example 3
Synthesis of 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-diisopropyl) aniline-2-ethyl ] pyridine nickel complex (Ni-A).
Take (DME)NiBr2(0.17g,0.54mmol) and 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-diisopropyl) aniline-2-ethyl]Pyridine (0.21g,0.27mmol) was charged to a Schlenk flask, CH was added2Cl2(20mL), the mixture was stirred at room temperature for 12 h. The resulting suspension was filtered, the solvent was spun off, the resulting powder was washed with ether (2X 10mL), then dried under vacuum at room temperature to give a brown solid, Ni-A (0.21g, 67%). Elemental analysis results: c, 52.78; h, 5.01; n, 4.65; found is C, 52.38; h, 4.69; n, 4.57; MALDI-TOF-MS (m/z) calcd for C53H60Br2N4Ni2O: 1042.1841; found 1042.1324[ M-2 Br]+。
Example 4
Synthesis of 9, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-dimethyl) aniline-2-ethyl ] pyridine nickel complex (Ni-B).
The procedure is as above, 9-dimethyl-9-xanthene-4, 4' -bis [2- (2, 6-dimethyl) aniline-2-ethyl is added]Pyridine (0.18g,0.27mmol) gave a brown solid powder, i.e., Ni-B (0.23g, 70%). Elemental analysis results: c, 49.41; h, 4.05; n, 5.12; found is C, 49.38; h, 3.69; n, 5.47; MALDI-TOF-MS (m/z): calcd for C45H44Br2N4Ni2O:930.0569；found:930.1324[M–2Br]+。
Example 5
To a 350mL thick-walled pressure-resistant glass vessel, 0.2mL MAO, 20mL toluene, and a magnetic stirrer were added in a glove box. A pressure bottle was connected to the high pressure polymerization line and the solution was degassed. The vessel was warmed to the desired temperature (20 ℃,40 ℃ and 60 ℃ respectively) using an oil bath and allowed to equilibrate for 5 minutes. Then dissolved in 2mL CH by a 2.5mL syringe under the protection of ethylene gas atmosphere2Cl2The nickel complex (5. mu. mol) in examples 3 to 4 of (1) was injected into the polymerization system. The reactor was pressurized and maintained at 4.0atm of ethylene with rapid stirring. After half an hour, the pressure was released and the reaction was stopped in acidified methanol (methanol/HCl 100/3). The polymer obtained was washed thoroughly with methanol and at 40 deg.CVacuum drying for 24 hours.
TABLE 1 ethylene polymerization with catalysts under different temperature gradientsa
aPolymerization conditions Ni 5. mu. mol; Al/Ni 500; toluene is 20 mL; dichloromethane ═ 20 mL; the time is 30 min;bactivity 10 ═ 105g·mol-1·h-1；cMolecular weight is g/mol; molecular weight was determined by high temperature GPC.
The oligomerization high-branching degree polyethylene is used in commercial 0# diesel oil for pour point depression experiment, the addition amount of the polyethylene is 0.3 percent, wherein the pour point of the 0# diesel oil is 0, and the cold filter plugging point is 3 ℃. The results are shown in Table 2 below, which can effectively reduce the freezing point and cold filter plugging point of diesel oil.
TABLE 2 pour point depressant test results
Claims (8)
1. A binuclear xanthene bridged amido-nickel pyridine catalyst is characterized in that: the catalyst has a structure shown in a formula (I):
wherein R is independently methyl or isopropyl.
2. A method for preparing the binuclear xanthene bridged amino-nickel pyridine catalyst according to claim 1, which comprises the following steps: the preparation method of the catalyst comprises the following steps:
(1) mixing the components in a molar ratio of 3-4:10 boric acid compound A and aniline compound B are mixed in an organic solvent, Pd (dba) is added2And triphenylphosphine under stirring at room temperature for 12-24h to form a diamine compound C, wherein Pd (dba)2And triphenylphosphine in an amount ofRespectively accounting for 20 percent and 10 percent of the mass of the boric acid compound A;
wherein R is independently methyl or isopropyl;
(2) heating diamine compound C and aldehyde compound D in a molar ratio of 1:6-7 in an organic solvent under the catalysis of organic acid, and carrying out reflux reaction for 12-24h to form ligand E:
wherein R is independently methyl or isopropyl;
(3) heating and refluxing ligand E and trimethylaluminum in a molar ratio of 1:6 in an organic solvent for 5-10h under the catalysis of organic acid to form ligand F:
wherein R is independently methyl or isopropyl;
(4) ligand F and (DME) NiBr in a molar ratio of 1:2 at room temperature2Reacting the compound in an organic solvent to obtain the catalyst with a structure shown in a formula (I), wherein DME (1, 2-dimethoxyethane):
wherein R is independently methyl or isopropyl.
3. The method for preparing the binuclear xanthene bridged amino-nickel pyridine catalyst according to claim 2, wherein the method comprises the following steps: the organic acid in the steps (2) and (3) is formic acid, acetic acid, p-toluenesulfonic acid or camphorsulfonic acid.
4. The method for preparing the binuclear xanthene bridged amino-nickel pyridine catalyst according to claim 2, wherein the method comprises the following steps: and (3) the organic solvent in the steps (1) to (4) is one or more of toluene, xylene, chlorobenzene, tetrahydrofuran, dichloromethane and ethanol.
5. The use of the binuclear xanthene bridged amino-nickel pyridine catalyst prepared by the method according to claim 2, wherein the binuclear xanthene bridged amino-nickel pyridine catalyst comprises the following steps: the catalyst is used for catalyzing ethylene oligomerization to prepare high-branching-degree polyethylene.
6. The use of the dinuclear xanthene bridged amino-nickel pyridine catalyst according to claim 5, wherein: the method for preparing the polyethylene with high branching degree by catalyzing ethylene oligomerization by using the catalyst comprises the following steps: adding methyl aluminoxane cocatalyst and aromatic hydrocarbon solvent into thick-wall pressure-resistant glass container under anhydrous and oxygen-free conditions, stirring, connecting the thick-wall pressure-resistant glass container with ethylene pipeline, degassing the solution, heating, introducing ethylene gas, and dissolving in CH2Cl2The nickel complex catalyst of the formula (I) is injected into a polymerization system, reacts under rapid stirring, and after the reaction is finished, the pressure is released and the reaction is stopped in acidified methanol to prepare the polyethylene.
7. The use of the dinuclear xanthene bridged amino-nickel pyridine catalyst according to claim 6, wherein: the reaction temperature is 0-80 ℃; the reaction time is 0.5-2 h; the ethylene pressure is 1-5 atm.
8. The use of the dinuclear xanthene bridged amino-nickel pyridine catalyst according to claim 6, wherein: the prepared polyethylene has the molecular weight of 1000-4000 and the branching degree of more than 80, and is used as a diesel pour point depressant.
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