CN119406454A - A phosphorus-containing porous organic polymer supported nickel catalyst and preparation method thereof - Google Patents
A phosphorus-containing porous organic polymer supported nickel catalyst and preparation method thereof Download PDFInfo
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- CN119406454A CN119406454A CN202411305074.6A CN202411305074A CN119406454A CN 119406454 A CN119406454 A CN 119406454A CN 202411305074 A CN202411305074 A CN 202411305074A CN 119406454 A CN119406454 A CN 119406454A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 73
- 239000011574 phosphorus Substances 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 16
- -1 phosphorous acid diester compound Chemical class 0.000 claims abstract description 7
- 229920005604 random copolymer Polymers 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011261 inert gas Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 125000001424 substituent group Chemical group 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- 229940126214 compound 3 Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229940125904 compound 1 Drugs 0.000 claims description 6
- 229940125782 compound 2 Drugs 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 5
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 claims description 5
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 5
- 238000010791 quenching Methods 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 3
- NLLMRAQUKLLMHE-UHFFFAOYSA-M magnesium;ethenylbenzene;bromide Chemical compound [Mg+2].[Br-].C=CC1=CC=[C-]C=C1 NLLMRAQUKLLMHE-UHFFFAOYSA-M 0.000 claims description 3
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005052 trichlorosilane Substances 0.000 claims description 3
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 claims 2
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 claims 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000013309 porous organic framework Substances 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- JRTIUDXYIUKIIE-KZUMESAESA-N (1z,5z)-cycloocta-1,5-diene;nickel Chemical compound [Ni].C\1C\C=C/CC\C=C/1.C\1C\C=C/CC\C=C/1 JRTIUDXYIUKIIE-KZUMESAESA-N 0.000 description 3
- DFCWBHWOHAWROH-UHFFFAOYSA-N 2,2-diphenylethyl dihydrogen phosphite Chemical compound C=1C=CC=CC=1C(COP(O)O)C1=CC=CC=C1 DFCWBHWOHAWROH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- ZBQUMMFUJLOTQC-UHFFFAOYSA-L dichloronickel;3-diphenylphosphanylpropyl(diphenyl)phosphane Chemical compound Cl[Ni]Cl.C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 ZBQUMMFUJLOTQC-UHFFFAOYSA-L 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- KVRSDIJOUNNFMZ-UHFFFAOYSA-L nickel(2+);trifluoromethanesulfonate Chemical compound [Ni+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F KVRSDIJOUNNFMZ-UHFFFAOYSA-L 0.000 description 3
- DJLBVUYUIACDIU-UHFFFAOYSA-N tris(4-ethenylphenyl)phosphane Chemical compound C1=CC(C=C)=CC=C1P(C=1C=CC(C=C)=CC=1)C1=CC=C(C=C)C=C1 DJLBVUYUIACDIU-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000013354 porous framework Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JVSFQJZRHXAUGT-UHFFFAOYSA-N 2,2-dimethylpropanoyl chloride Chemical compound CC(C)(C)C(Cl)=O JVSFQJZRHXAUGT-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- BZRLFVYTFDNRJT-UHFFFAOYSA-N [P]C=C Chemical compound [P]C=C BZRLFVYTFDNRJT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/1414—Esters of phosphorous acids with arylalkanols
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/143—Esters of phosphorous acids with unsaturated acyclic alcohols
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/141—Esters of phosphorous acids
- C07F9/144—Esters of phosphorous acids with cycloaliphatic alcohols
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention relates to the technical field of catalysts, and particularly discloses a phosphorus-containing porous organic polymer supported nickel catalyst which is prepared from a Ni precursor and a phosphorus-containing porous organic polymer, wherein the mass fraction of Ni in the catalyst is 0.1% -10%, and the phosphorus-containing porous organic polymer is a random copolymer and has a structural general formula I, and a preparation method and application thereof. After the porous organic polymer containing the phosphorus ligand and the transition metal salt form the catalyst, the catalyst can be used for efficiently catalyzing and synthesizing the phosphorous acid diester compound, can be recycled after the reaction is finished, and can not obviously reduce the performance in the cyclic catalysis process.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a phosphorus-containing porous organic polymer supported nickel catalyst and a preparation method thereof.
Background
In recent decades, porous organic polymers are widely applied to the fields of photoelectric conversion, gas adsorption and separation, catalysis, energy storage and conversion and the like due to the characteristics of high specific surface area, controllable pore structure, good chemical and thermal stability, easy surface functionalization and the like, and are emerging materials with great development potential. Among porous materials, scientists have first studied inorganic porous materials such as activated carbon, zeolite, porous silica, and the like. The material has larger specific surface area and higher porosity, so the material is widely used as a catalytic material and an adsorption separation material, but has the defects of single synthesis condition, difficult functionalization, poor preparation regulation and control and the like, so the application of the material is limited to a certain extent. The porous organic framework material is used as a supporting substrate, and is used for catalysis, because the porous organic framework material generally has special properties, such as high specific surface area, which can provide more catalytic sites for the catalytic reaction, on the other hand, the porous organic framework is insoluble in general solvents, thus playing an important role in metal recovery and recycling, and secondly, the porous organic framework is easy to modify, can accommodate various metals, functional groups or metal coordination sites, and enriches the diversity of the catalytic reaction. Under the background, in order to meet the continuous improvement of the requirements of the organic porous framework material and the continuous understanding of the structure of the organic porous framework material, the design and development of the functional porous organic framework material are of great significance.
Disclosure of Invention
The first object of the invention is to provide a porous organic polymer supported nickel catalyst containing phosphorus, which not only can be used for efficiently catalyzing and synthesizing a phosphorous diester compound, but also can be recycled after the reaction is finished, and the performance of the catalyst is not reduced in the cyclic catalysis process.
It is a second object of the present invention to provide a process for preparing the catalyst as defined above.
It is a third object of the present invention to provide the use of the above catalyst.
The aim of the invention is realized by the following technical scheme:
The phosphorus-containing porous organic polymer supported nickel catalyst is prepared from a Ni precursor and a phosphorus-containing porous organic polymer, wherein the mass fraction of Ni in the catalyst is 0.1% -10%, and the phosphorus-containing porous organic polymer is a random copolymer and has the following structural formula I:
In the general structural formula I, a is methylene of 0-5, m is the molar content of phosphorus-containing polymerized monomers, n is the molar content of comonomers, m is 1:0-100, but subscripts m and n do not represent the linking sequence of the monomers, the linking sequence of the monomers can be unfixed, the polymer is a random polymer, and R is
A monomer unit.
Preferably, the Ni precursor is selected from one or more of Ni(acac)2、NiCl2、Ni(PPh3)2Cl2、Ni(dppp)Cl2、Ni(dppf)Cl2、Ni(OTf)2、Ni(BINAP)Cl2、Ni(COD)2、Ni(OAc)2, preferably NiCl 2, and m: n is 1:1-20.
The preparation method of the phosphorus-containing porous organic polymer supported nickel catalyst comprises the steps of placing a Ni precursor and a phosphorus-containing porous organic polymer into a solvent under the protection of inert gas, stirring at 0-200 ℃ to enable the Ni precursor to be anchored on the phosphorus-containing porous organic polymer through coordination, and then removing the solvent to obtain the catalyst;
the phosphorus-containing porous organic polymer has the following structural general formula I:
in the structural general formula I, a is methylene of 0-5, m is the molar content of phosphorus-containing polymerized monomers, n is the molar content of comonomers, m is 1:0-100, and R is A monomer unit.
Preferably, the Ni precursor is selected from one or more of Ni(acac)2、NiCl2、Ni(PPh3)2Cl2、Ni(dppp)Cl2、Ni(dppf)Cl2、Ni(OTf)2、Ni(BINAP)Cl2、Ni(COD)2、Ni(OAc)2, the Ni loading mass fraction is 0.1% -10% based on the weight of the final catalyst, calculated according to the element Ni, the solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene and toluene, the stirring temperature is 25-100 ℃, the stirring time is 12-48h, and the inert gas is argon or nitrogen.
Further preferably, m is 1:1-20, the Ni precursor is NiCl 2, the Ni loading mass fraction is 0.1% -1% based on the weight of the final catalyst, the stirring time is 24-36h, the solvent is tetrahydrofuran or toluene, and the inert gas is argon.
Further, the preparation method of the polymer with the structural general formula I comprises the steps of under the protection of inert gas, functionalizing the vinyl phosphorus-containing polymer monomerDissolving the polymer and a comonomer based on a substituent R in tetrahydrofuran, adding a free radical initiator azodiisobutyronitrile, and stirring for reaction for 24-48 hours to obtain a polymer with a structural general formula I;
the comonomer based on substituent R is
Preferably, in the preparation method of the polymer with the general structural formula I, the molar ratio of the phosphorus-containing polymerized monomer to the comonomer based on the substituent R is 1:0-100, the molar amount of the azodiisobutyronitrile is 0.1-5% of the molar amount of vinyl in the raw material, the temperature of the stirring reaction is 60-150 ℃, and the inert gas is argon or nitrogen.
Further preferably, in the preparation method of the polymer with the structural general formula I, the molar ratio of the phosphorus-containing polymerized monomer to the comonomer based on the substituent R is 1:1-20, the temperature of the stirring reaction is 80-100 ℃, and the inert gas is argon.
Further, the preparation method of the phosphorus-containing polymerized monomer comprises the following steps:
Step 1, dropwise adding phosphorus trichloride into tetrahydrofuran containing (4-vinylphenyl) magnesium bromide under the stirring condition of 0 ℃, heating to room temperature, stirring for reacting overnight, extracting with ethyl acetate after quenching, removing solvent under reduced pressure, and separating by column chromatography to obtain a compound 1, wherein an eluent is petroleum ether and ethyl acetate mixed solution with the volume ratio of 50:1;
step 2, adding the compound 1, dibromoalkane and acetonitrile into a reactor, carrying out reflux stirring reaction for 24 hours at 90 ℃, adding methanol and 6M KOH after removing the solvent under reduced pressure, continuing the reflux stirring reaction for 24 hours, cooling, removing the solvent under reduced pressure, and separating by column chromatography to obtain a compound 2, wherein the eluent is methylene dichloride and methanol mixed solution with the volume ratio of 50:1;
And 3, under the protection of inert gas, adding the compound 2 into a reactor, adding toluene for dissolution, dropwise adding trichlorosilane, refluxing and stirring at 110 ℃ for reaction for 12 hours, then adding 2M NaOH for quenching, extracting with ethyl acetate, removing the solvent under reduced pressure, separating by column chromatography to obtain the compound 3, wherein the eluent is petroleum ether and ethyl acetate mixed solution with the volume ratio of 50:1, and thus the vinyl functionalized phosphorus-containing polymer monomer can be obtained.
The application of the porous organic polymer supported nickel catalyst containing phosphorus in the catalytic synthesis of a phosphorous acid diester compound.
Compared with the prior art, the invention has the following advantages:
The porous organic polymer supported nickel catalyst containing the phosphorus ligand is used for efficiently catalyzing and synthesizing a phosphorous diester compound, has mild reaction conditions, can reach 94% of yield, is suitable for large-scale production, has practical value, can be recycled after the reaction is finished, has no reduction in performance in the cyclic catalysis process, can reduce the production cost, and adds a new catalyst for heterogeneous catalysis.
Drawings
FIG. 1 is a structural unit structure of a phosphorus-containing porous organic polymer supported nickel catalyst A in example 1;
FIG. 2 is a 1 H spectrum of vinyl functionalized phosphorus-containing polymerized monomer compound 3 in deuterated chloroform;
FIG. 3 is a 13 C spectrum of vinyl functionalized phosphorus-containing polymerized monomer compound 3 in deuterated chloroform;
FIG. 4 is a 31 P spectrum of vinyl functionalized phosphorus-containing polymerized monomer compound 3 in deuterated chloroform;
FIG. 5 is a 1 H spectrum of tris (4-vinylphenyl) phosphorus comonomer L3 in deuterated chloroform;
FIG. 6 is a 13 C spectrum of tris (4-vinylphenyl) phosphorus comonomer L3 in deuterated chloroform;
FIG. 7 is a 31 P spectrum of tris (4-vinylphenyl) phosphorus comonomer L3 in deuterated chloroform;
FIG. 8 is a preparation route diagram of the phosphorus-containing porous organic polymer catalyst A in example 1;
FIG. 9 is an XRD characterization of the phosphorus-containing porous organic polymer catalyst A of example 1
FIG. 10 is a FT-IR characterization of a phosphorus-containing porous organic polymer catalyst A of example 1;
FIG. 11 is a BET characterization of the phosphorus-containing porous organic polymer catalyst A of example 1;
FIG. 12 is a pore size distribution plot of the phosphorus-containing porous organic polymer catalyst A of example 1;
FIG. 13 is an SEM characterization of a phosphorus-containing porous organic polymer catalyst A of example 1;
FIG. 14 is a TEM characterization of the phosphorus-containing porous organic polymer catalyst A of example 1.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and explanation only and is not intended to limit the present invention.
Unless otherwise indicated, the starting materials in the examples of the present invention were purchased commercially, e.g., an Naiji, piobtained, etc., from reagent companies, without further purification.
The preparation method of part of the products in the examples is as follows:
1. vinyl functionalized phosphorus-containing polymeric monomers The preparation method of (2) is as follows:
step 1, dropwise adding 20.0 millimoles of phosphorus trichloride into 40 milliliters of tetrahydrofuran containing 80.0 millimoles of (4-vinylphenyl) magnesium bromide under the condition of stirring at 0 ℃, heating to room temperature, stirring and reacting overnight, quenching, extracting with ethyl acetate, removing a solvent under reduced pressure, and separating by column chromatography to obtain a compound 1, wherein an eluent is petroleum ether and ethyl acetate mixed solution with the volume ratio of 50:1;
step 2, adding 10.0 mmol of compound 1, 20.0 mmol of dibromoalkane and 20 ml of acetonitrile into a reactor, carrying out reflux stirring reaction for 24 hours at 90 ℃, adding 10 ml of methanol and 6M KOH after removing the solvent under reduced pressure, continuing the reflux stirring reaction for 24 hours, cooling, removing the solvent under reduced pressure, separating by column chromatography to obtain compound 2, wherein the eluent is methylene dichloride and methanol mixed solution with the volume ratio of 50:1;
And 3, under the protection of inert gas, adding 1.0 millimole of compound 2 into a reactor, adding toluene for dissolution, dripping 24.0 millimole of trichlorosilane, refluxing and stirring at 110 ℃ for reaction for 12 hours, then adding 2M NaOH for quenching, extracting with ethyl acetate, removing the solvent under reduced pressure, separating by column chromatography to obtain compound 3, wherein the eluent is petroleum ether and ethyl acetate mixed solution with the volume ratio of 50:1, and thus the vinyl functionalized phosphorus-containing polymer monomer can be obtained.
2. Polymers of the general structural formula IThe preparation method of (2) is as follows:
under the protection of inert gas, vinyl functionalized phosphorus-containing polymeric monomer Dissolving the polymer with comonomer based on substituent R in tetrahydrofuran, adding free radical initiator azodiisobutyronitrile, stirring and reacting for 24-48h to obtain polymer with the general structural formula I, wherein the reaction formula is as follows:
The molar ratio of the phosphorus-containing polymerization monomer to the comonomer based on the substituent R is 1:0-100, preferably 1:1-20, the molar amount of the azodiisobutyronitrile is 0.1-5% of the molar amount of the vinyl in the raw material, the temperature of the stirring reaction is 60-150 ℃, preferably 80-100 ℃, the inert gas is argon or nitrogen, preferably argon, and the comonomer based on the substituent R is
In the general structural formula I, a is methylene of 0-5, m is the molar content of phosphorus-containing polymerized monomers, n is the molar content of comonomers, m is 1:0-100, preferably 1:1-20, but the subscripts m and n do not represent the linking sequence of the monomers, the linking sequence of the monomers can be unfixed and is a random polymer, and R is A monomer unit.
3. The preparation method of the phosphorus-containing porous organic polymer supported nickel catalyst comprises the following steps:
under the protection of inert gas, a Ni precursor and a phosphorus-containing porous organic polymer (polymer with a structural formula I) are placed into a solvent, and are stirred at a temperature of between 0 and 200 ℃ to enable the Ni precursor to be anchored on the phosphorus-containing porous organic polymer through coordination, and then the solvent is removed to prepare the phosphorus-containing porous organic polymer supported nickel catalyst.
The Ni precursor is selected from one or more of Ni(acac)2、NiCl2、Ni(PPh3)2Cl2、Ni(dppp)Cl2、Ni(dppf)Cl2、Ni(OTf)2、Ni(BINAP)Cl2、Ni(COD)2、Ni(OAc)2, preferably NiCl 2, the Ni loading mass fraction is 0.1% -10%, preferably 0.1% -1% calculated according to the element Ni based on the weight of the final catalyst, the solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, toluene, preferably tetrahydrofuran or toluene, the stirring temperature is preferably 25-100 ℃, the stirring time is 12-48h, preferably 24-36h, and the inert gas is argon or nitrogen, preferably argon.
Example 1
Mixing 0.9 g of vinyl functionalized phosphorus-containing polymeric monomer (namely compound 3) and 5.92 g of comonomer L3 under the protection of inert gas argon at room temperature, dissolving in 120m L g of tetrahydrofuran, adding 0.16 g of free radical initiator azodiisobutyronitrile into the solution, stirring for 2 hours, transferring the stirred solution to an autoclave with stirring, continuing stirring reaction, polymerizing for 24 hours under the protection of 100 ℃ and nitrogen by utilizing a solvothermal polymerization method, cooling the polymerized solution to the room temperature, and vacuumizing the solvent under the room temperature condition to obtain the phosphorus-containing organic polymer carrier. 62.8mg of nickel chloride is weighed and dissolved in 100.0ml of tetrahydrofuran solvent, 1.0 g of phosphorus-containing organic polymer carrier obtained by copolymerization is added, the mixture is stirred for 24 hours under the protection of inert gas argon at 25 ℃, and then the solvent is vacuumized under the room temperature condition, so that the multiphase phosphorus-containing porous organic polymer supported nickel catalyst A is obtained.
Example 2
In example 2, the procedure was followed in the same manner as in example 1, except that 5.92g of L1 comonomer was used instead of 5.92g of L3 comonomer. The obtained phosphorus-containing porous organic polymer in-situ encapsulation nickel catalytic material is denoted as a catalyst B.
Example 3
In example 3, the procedure was followed in the same manner as in example 1, except that 5.92g of the L2 comonomer was used instead of 5.92g of the L3 comonomer. The obtained phosphorus-containing porous organic polymer in-situ encapsulation nickel catalytic material is denoted as a catalyst C.
From the XRD characterization diagram of FIG. 9 and the SEM characterization diagram of FIG. 13, it can be seen that the phosphorus-containing porous organic polymer of the general structural formula I is a random copolymer, and micropores and mesopores exist in the pores, which is more beneficial to catalytic reaction.
Example 4
Taking the catalyst A in example 1 as an example, the reusability of the phosphorus-containing porous organic polymer in-situ encapsulated nickel catalytic material in the catalytic synthesis of diphenylethyl phosphite (which belongs to a phosphorous diester compound, and phosphorous diester [ (RO) 2 P (O) H ] is a main intermediate used in fine and industrial organophosphorus chemistry) is illustrated.
30Mg of the catalyst A prepared above was charged into a 10m L-reaction tube, and 0.0176g (0.2 mmol) of sodium hypophosphite, 0.122g (1.0 mmol) of phenethyl alcohol, 74uL (0.6 mmol) of trimethylacetyl chloride and 3.0mL of acetonitrile were added, and after sealing, the reaction was carried out after heating to 120℃and then reaction was carried out for 12 hours, to obtain diphenylethyl phosphite. After the reaction is finished, the reaction tube is cooled to room temperature, the solid catalyst is centrifugally separated, and is washed three times by methanol and distilled water respectively, and the dried catalyst is used for recycling. The reaction solution was added with triphenylphosphine as an internal standard and analyzed by nuclear magnetic yield. The reaction data for the catalyst reuse are shown in table 1. As can be seen from Table 1, the catalytic material prepared by the invention can be reused for five times, and the catalytic activity can be well maintained.
Table 1 reusability of catalyst a of example 1 in a reaction for the synthesis of diphenylethyl phosphite
Examples 5 to 18
In examples 5-18, the procedure was followed as in example 4, except that 1.0mmol of the different alcohol substrate was used instead of 1.0mmol of phenethyl alcohol. The reaction results for the different alcohol substrates are shown in Table 2. As can be seen from table 2, the catalyst prepared according to the present invention can be applied to the reaction of different alcohols, and exhibits excellent catalytic activity.
TABLE 2 catalytic Properties of catalyst A of example 1 in different alcohol substrates
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
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