CN107899614A - A kind of double-core xanthenes bridging amido pyridine Raney nickel and its preparation method and application - Google Patents
A kind of double-core xanthenes bridging amido pyridine Raney nickel and its preparation method and application Download PDFInfo
- Publication number
- CN107899614A CN107899614A CN201711155478.1A CN201711155478A CN107899614A CN 107899614 A CN107899614 A CN 107899614A CN 201711155478 A CN201711155478 A CN 201711155478A CN 107899614 A CN107899614 A CN 107899614A
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- China
- Prior art keywords
- xanthenes
- core
- double
- raney nickel
- pyridine
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000007868 Raney catalyst Substances 0.000 title claims abstract description 16
- 229910000564 Raney nickel Inorganic materials 0.000 title claims abstract description 16
- 150000003732 xanthenes Chemical group 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract description 6
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title abstract 3
- 125000003368 amide group Chemical group 0.000 title description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 amido pyridine Chemical compound 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 13
- 239000004698 Polyethylene Substances 0.000 claims abstract description 13
- 229920000573 polyethylene Polymers 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 239000003112 inhibitor Substances 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 5
- 150000004985 diamines Chemical class 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
- 238000003756 stirring Methods 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 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
- 238000000034 method Methods 0.000 claims description 4
- 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 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 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
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- 239000003849 aromatic solvent Substances 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 2
- 238000007872 degassing Methods 0.000 claims 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 16
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 8
- 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
- 230000000694 effects Effects 0.000 description 7
- 230000000994 depressogenic effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 150000003222 pyridines Chemical class 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 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
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-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
- 238000001914 filtration Methods 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000000843 powder Substances 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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 System
- 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
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- 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)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of new xanthenes bridging amido pyridine double-core Raney nickel and preparation method thereof, and use it for catalyzed ethylene polymerization and prepare low degree, the polyethylene of highly -branched degree, this double-core Raney nickel has higher heat endurance and catalytic activity, and it can effectively regulate and control the molecular weight and the degree of branching of polyethylene, obtained highly -branched degree, the polyethylene product of low degree can be used as diesel pour inhibitor, can be effectively reduced the condensation point and cold filter plugging point of diesel oil.
Description
Technical field
The invention belongs to catalytic field, and in particular to a kind of double-core xanthenes bridging amido-pyridine Raney nickel and its preparation
Method and application.
Background technology
The main reason for diesel oil loses flowability at low temperature is that the wax crystallization in diesel oil separates out, and it is brilliant to form wax.These waxes
Crystalline substance mushrooms out, and is bonded to mesh skeleton structure and diesel oil is wrapped in the inside, so that it loses flowability.It is suitable when adding
After pour-point depressant, although the precipitation of wax can not be prevented, it can weaken wax crystalline form by varying the size and shape of wax and reticulate
The ability of structure, so as to improve the mobile performance of diesel oil.
The diesel pour inhibitor of current domestic development is of less types, (the .AVS types such as Feng Lijuan, Zhang Zhiqing, Wang Fang such as Feng Lijuan
Performance [J] oilfield chemistries of diesel pour inhibitor, 2013,30 (4):586-589,593) 4 kinds have been synthesized using radical polymerization
Alkyl acrylate-vinyl acetate-styrene copolymer of different alkyl chain lengths, by measuring copolymer to diesel oil
Pour point depression drop filter effect finds that AVS-16 depression effeCts are preferable, condensation point of diesel oil can be made to reduce by 12 DEG C, but it is poor to drop filter effect；AVS-18
Drop filter effect is preferable, can make the cold filter plugging point of diesel oil reduce by 4 DEG C, and depression effeCt is also preferable.
(Wang Jingjing, Xie Chengxi, the development of Tan Jian .P (DBF-VA) type Copolymer As Diesel Fuel Cold Flow Improver such as Wang Jingjing
[J] Speciality Petrochemicals, 2006,23 (6):Dibehenyl fumarate-second 22-24.) has been synthesized with radical polymerization method
Vinyl acetate bipolymer, can make to spit Kazakhstan -10#、0#Cold filter point of diesel oil reduces by 10 DEG C and 7 DEG C respectively；Make Dushanzi 0#Diesel oil
Cold filter plugging point declines 12 DEG C；Kelamayi 0#Cold filter point of diesel oil declines 8 DEG C.
Above-mentioned pour-point depressant is mostly the copolymer of esters polymer or esters and alkene, and reaction temperature is higher, production
Cost is higher.
The content of the invention
The present invention provides a kind of double-core xanthenes bridging amido-pyridine Raney nickel, and the catalyst activity is high, polymerization
Reaction condition is gentle, with catalysed ethylene oligomerisation, can prepare the ethylene low polymer of highly -branched degree, which can directly make
For oil pour-point depressant, using ethene as raw material, production cost is low.
Double-core xanthenes bridging amido-pyridine Raney nickel provided by the invention is the structure shown in following formula (I)：
Wherein, R is independent methyl or isopropyl.
The preparation method of the catalyst includes the following steps：
(1) boronic acid compounds A and aniline compound B (excess) presses 3-4:10 molar ratio, mixes in organic solvent, adds
Enter Pd (dba)2(addition is the 10% of boronic acid compounds A for (addition is 20% (w) of boronic acid compounds A) and triphenylphosphine
(w)) 12h-24h is reacted in stirring at room temperature, forms diamine compound C：
Wherein, R is independent methyl or isopropyl.
(2) diamine compound C and aldehyde compound D presses 1:The molar ratio of 6-7 adds in organic solvent under organic acid catalysis
Hot back flow reaction 12-24h, forms ligand E：
Wherein, R is independent methyl or isopropyl.
(3) ligand E and trimethyl aluminium press 1:6 molar ratio is heated to reflux anti-in organic solvent under organic acid catalysis
5-10h is answered, forms ligand F：
Wherein, R is independent methyl or isopropyl.
(4) ligand F and (DME) NiBr at room temperature2Compound presses 1:2 molar ratio is reacted in a solvent, obtains formula (I)
The catalyst of shown structure.
Wherein, R is independent methyl or isopropyl.
Step (2) and step (3) described organic acid are one kind in formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid；
Step (1), step (2), step (3) and step (4) described organic solvent are toluene, dimethylbenzene, chlorobenzene, tetrahydrofuran, dichloro
One or more in methane.
Catalyst of the present invention prepares low polymerization degree for being catalyzed ethene, and the preparation method of high-branched polyethylene is：
Under the conditions of anhydrous and oxygen-free, co-catalyst MAO, aromatic solvent are added into the pressure-resistant glass container of heavy wall and is stirred.By pressure bottle
It is connected with ethene pipeline, and solution is deaerated, be heated to required temperature, is passed through ethylene gas, and be dissolved in CH2Cl2In formula
(I) in nickel complex as catalyst agent injection polymerization system, react under fast stirring.After reaction, pressure release and in the first of acidifying
Reaction is terminated in alcohol, polyethylene is made.
Wherein, the reaction temperature is 0-80 DEG C；The ethylene pressure is 1-5atm；The reaction time is 0.5-2h.
Double-core xanthenes bridging amido of the present invention-high-branched polyethylene made from the catalysis of pyridine Raney nickel is dropped as diesel oil
Solidifying agent, molecular weight of polyethylene are 1000~4000, and the degree of branching is more than 80.
Beneficial effect：Catalyst prepared by the present invention, its catalytic activity is high, and polymeric reaction condition is gentle, can be catalyzed
Ethylene oligomerization, can prepare the ethylene low polymer of highly -branched degree；Obtained oligomer can be used as oil pour-point depressant, using ethene as
Raw material produces pour-point depressant, and relative to the copolymer pour-point depressant of current esters polymer or esters and alkene, cost is than relatively low.
Embodiment
The particular content of the present invention has been illustrated in following embodiments, gives synthesis and the second of ligand and complex
The method of alkene polymerization.The wherein synthesis of complex, polymerization process are carried out under anhydrous and oxygen-free, all sensitive material storages
In glove box, all solvents are all by stringent dry water removal.Ethylene gas is purified by removing water deoxygenation pillar.If without spy
Different explanation, all raw materials directly use after buying.
It is as follows to characterize instrument：
Bruker 400MHz nuclear-magnetism instruments are used in nuclear-magnetism detection.Elemental analysis (Vario EL cube).Molecular weight and molecule
Amount distribution is measured by high temperature GPC.Mass spectrum Thermo LTQ Orbitrap XL (ESI+) or P-SIMS-Gly of
Bruker Daltonics Inc (EI+) are measured.
Embodiment 1：
9,9- dimethyl -9- xanthenes -4, the synthesis of 4 '-bis- [2- (2,6- diisopropyl) aniline -2- ethyls] pyridines, reaction equation
It is as follows.
Take the double boric acid (1.0g, 3.4mmol) of xanthenes, 1,6- diisopropyl para-bromoaniline (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
After the mixing of (7mL) and toluene (24mL), it is stirred overnight, after reaction stops, being extracted with ethyl acetate, NaCl at room temperature
Afterwards, dried with magnesium sulfate, be spin-dried for solvent, add 10mL recrystallizing methanols, filtered, it is dry, obtain pale solid 9,9- bis-
Methyl -9- xanthenes -4,4 '-bis- (2,6- diisopropyls) aniline (i.e. diamine compound C) (1.0g, 54%).
Take 9,9- dimethyl -9- xanthenes -4,4 '-bis- (2,6- diisopropyl) aniline (1.0g, 1.79mmol), 2- pyridine first
The p-methyl benzenesulfonic acid of aldehyde (1.30g, 12.1mmol) and 0.05 equivalent, after being dissolved in toluene (30mL), flow back 24h, during which passes through
Contact plate monitors the extent of reaction.After reaction, solvent is spin-dried for, 20ml methanol is added and is recrystallized, mixture is at -20 DEG C
Yellow solid, filtering, vacuum drying obtain 9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- diisopropyl) benzene imines] pyrroles
Pyridine, yield 90% (1.21g).
Take 9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- diisopropyl) benzene imines] pyridines (1.21g, 2mmol),
The p-methyl benzenesulfonic acid of trimethyl aluminium (12mmol) and 0.1 equivalent, is dissolved in toluene (25mL).In N2Flow back under atmosphere protection
After 5h, after reaction stops, 1N ice NaOH solutions are added.Organic layer is washed with saturation NaCl solution twice, Na2SO4It is dry, it is spin-dried for
Solvent, adds a large amount of n-hexanes afterwards, and filtering, gained white solid washs 3 times using n-hexane repeatedly, after vacuum drying to obtain the final product
9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- diisopropyl) aniline -2- ethyls] pyridines, 89% (1.12g).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),3.03(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]+.
Embodiment 2
9,9- dimethyl -9- xanthenes -4, the synthesis of 4 '-bis- [2- (2,6- dimethyl) aniline -2- ethyls] pyridines, reaction equation is such as
Under.
Step is same as above, and input 1,6- dimethylatedρ-bromoanilines (2.0g, 10mmol), finally obtain 9,9- dimethyl -9- and account for
Ton -4,4 '-bis- [2- (2,6- dimethyl) aniline -2- ethyls] pyridines, 84% (1.01g).1H NMR(500MHz,CDCl3,
ppm):δ 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,
CHCH3)；13C{1H}NMR(125MHz,CDCl3,ppm):δ164.2,149.2,147.5,143.9,136.2,130.4,
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-CH3)；HRMS(m/z):calcd for C45H47N4O:
659.3750；found:659.4578[M+H]+.
Embodiment 3
9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- diisopropyls) aniline -2- ethyls] pyridine nickel compositions
Synthesize (Ni-A).
Take (DME) NiBr2(0.17g, 0.54mmol) and 9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- diisopropyls
Base) aniline -2- ethyls] pyridine (0.21g, 0.27mmol) add Schlenk flasks in, add CH2Cl2(20mL), by mixture
Be stirred at room temperature 12 it is small when.The suspension produced is filtered, is spin-dried for solvent, gained powder is washed with ether (2 × 10mL), then
Vacuum drying obtains brown solid at room temperature, is Ni-A (0.21g, 67%).Elemental analysis result：C,52.78；H,
5.01；N,4.65；found:C,52.38；H,4.69；N,4.57；MALDI-TOF-MS(m/z):calcd for
C53H60Br2N4Ni2O:1042.1841；found:1042.1324[M–2Br]+.
Embodiment 4
The conjunction of 9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- dimethyl) aniline -2- ethyls] pyridine nickel compositions
Into (Ni-B).
Step is same as above, and has put into 9,9- dimethyl -9- xanthenes -4,4 '-bis- [2- (2,6- dimethyl) aniline -2- ethyls] pyrroles
Pyridine (0.18g, 0.27mmol), obtains brown solid powder, is Ni-B (0.23g, 70%).Elemental analysis result：C,
49.41；H,4.05；N,5.12；found:C,49.38；H,3.69；N,5.47；MALDI-TOF-MS(m/z):calcd for
C45H44Br2N4Ni2O:930.0569；found:930.1324[M–2Br]+。
Embodiment 5
0.2mL MAO, 20mL toluene and magnetic agitation are added into the pressure-resistant glass container of 350mL heavy walls in glove box
Son.Pressure bottle is connected to high pressure polymerisation pipeline, and solution is deaerated.Container is warmed to required temperature (respectively using oil bath
For 20 DEG C, 40 DEG C and 60 DEG C) and it is balanced 5 minutes.Then will be molten under ethylene gas atmosphere protection by 2.5ml syringes
Solution is in 2mL CH2Cl2Embodiment 3-4 in nickel complex (5 μm of ol) injection polymerization system in.Under fast stirring, will react
Device pressurizes and is maintained at the ethene of 4.0atm.After half an hour, pressure release simultaneously terminates (methanol/HCl=100/ in the methanol of acidifying
3).The polymer obtained is fully washed with methanol and when 40 DEG C of vacuum drying 24 is small.
Vinyl polymerization of 1 catalyst of table under different temperatures gradienta
aPolymerizing condition:Ni=5 μm of ol；Al/Ni=500；Toluene=20mL；Dichloromethane=20mL；Time=30min；b
Activity=105g·mol-1·h-1；cMolecular weight=g/mol；Molecular weight is measured by high temperature GPC.
Above-mentioned oligomeric high-branched polyethylene is used to carry out pour point depression experiment in commercially available 0# diesel oil, polyethylene addition is
0.3%, the condensation point of wherein 0# diesel oil is 0, cold filter plugging point is 3 DEG C.The result is shown in table 2 below, can be effectively reduced the condensation point of diesel oil with it is cold
Filter point.
2 pour point depression experimental result of table
Claims (8)
- A kind of 1. double-core xanthenes bridging amido-pyridine Raney nickel, it is characterised in that：The catalyst is the knot shown in formula (I) Structure：Wherein, R is independent methyl or isopropyl.
- 2. a kind of preparation method of double-core xanthenes bridging amido-pyridine Raney nickel as claimed in claim 1, its feature exist In：The preparation method step of the catalyst is as follows：(1) it is 3-4 by molar ratio：10 boronic acid compounds A is mixed in organic solvent with aniline compound B, adds Pd (dba)2 Stir reaction 12h-24h at room temperature with triphenylphosphine, form diamine compound C, wherein Pd (dba)2With the addition of triphenylphosphine Amount is respectively the 20% and 10% of the quality of boronic acid compounds A；Wherein, R is independent methyl or isopropyl；(2) it is 1 by molar ratio:The diamine compound C and aldehyde compound D of 6-7 is heated in organic solvent under organic acid catalysis Back flow reaction 12h-24h, forms ligand E：Wherein, R is independent methyl or isopropyl；(3) it is 1 by molar ratio:6 ligand E with trimethyl aluminium under organic acid catalysis, heating reflux reaction in organic solvent 5h-10h, forms ligand F：Wherein, R is independent methyl or isopropyl；(4) at room temperature by molar ratio be 1:2 ligand F and (DME) NiBr2Compound is reacted in organic solvent, obtains formula (I) The catalyst of shown structure, wherein, DME=1,2- dimethoxy-ethanes：Wherein, R is independent methyl or isopropyl.
- 3. the preparation method of double-core xanthenes bridging amido-pyridine Raney nickel as claimed in claim 2, it is characterised in that：Step Suddenly (2) and (3) described organic acid are formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid.
- 4. the preparation method of double-core xanthenes bridging amido-pyridine Raney nickel as claimed in claim 2, it is characterised in that：Step Suddenly (1)-step (4) described organic solvent for toluene, dimethylbenzene, chlorobenzene, tetrahydrofuran, dichloromethane, one kind in ethanol or It is a variety of.
- 5. a kind of application of double-core xanthenes bridging amido-pyridine Raney nickel prepared by method as claimed in claim 2, its feature It is：The catalyst prepares high-branched polyethylene for catalysed ethylene oligomerisation.
- 6. the application of double-core xanthenes bridging amido-pyridine Raney nickel as claimed in claim 5, it is characterised in that：It is described to urge Agent is used for catalysed ethylene oligomerisation and prepares the method for high-branched polyethylene：Under the conditions of anhydrous and oxygen-free, to the pressure-resistant glass of heavy wall Co-catalyst methylaluminoxane and aromatic solvent are added in glass container and is stirred, pressure bottle is connected with ethene pipeline, by solution Degassing, heating, is passed through ethylene gas, and be dissolved in CH2Cl2In the agent of formula (I) nickel complex as catalyst injection polymerization system in, React under fast stirring, after reaction, pressure release simultaneously terminates in the methanol of acidifying, and polyethylene is made.
- 7. the application of double-core xanthenes bridging amido-pyridine Raney nickel as claimed in claim 6, it is characterised in that：It is described anti- It is 0-80 DEG C to answer temperature；The reaction time is 0.5-2h；The ethylene pressure is 1-5atm.
- 8. the application of double-core xanthenes bridging amido-pyridine Raney nickel as claimed in claim 6, it is characterised in that：The system The molecular weight of polyethylene obtained is 1000~4000, and the degree of branching is more than 80, as diesel pour inhibitor.
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| US20100298618A1 (en) * | 2007-11-23 | 2010-11-25 | Vugar Aliyev | Catalyst composition and process for oligomerization of ethylene |
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