CN117380283A - Preparation of heterogeneous iridium-based catalyst and method for producing aldehyde by hydroformylation - Google Patents
Preparation of heterogeneous iridium-based catalyst and method for producing aldehyde by hydroformylation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 22
- 229910052741 iridium Inorganic materials 0.000 title claims description 16
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title claims description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 3
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 13
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-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 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- -1 triphenylphosphine compound Chemical class 0.000 claims description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 238000005580 one pot reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 3
- FTDZECHQBVIHKZ-UHFFFAOYSA-N 5,5-dibromo-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(Br)(Br)CC=C1C1=CC=CC=C1 FTDZECHQBVIHKZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910007926 ZrCl Inorganic materials 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000012718 coordination polymerization Methods 0.000 claims description 2
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 2
- 239000013309 porous organic framework Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 15
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention develops a heterogeneous Ir-based catalyst for hydroformylation of propylene. Compared with Rh-based catalyst, the process cost is reduced; compared with a homogeneous Ir-based catalyst, the recoverable performance is improved. In addition, the heterogeneous Ir-based catalyst has a linear aldehyde/branched aldehyde ratio of less than 1, excellent branched chain selectivity and catalytic reaction efficiency, and a highest catalyst conversion number (TON) of 21916, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of organic chemical industry, in particular to an iridium-based catalyst, a preparation method thereof and a method for producing aldehyde by catalyzing acrolein.
Background
Hydroformylation is an important class of reactions in the chemical industry, typically using olefins and synthesis gas (CO/H) 2 ) As reactants, the product of the hydroformylation is a carbon chain extended aldehyde which can be further used to prepare a range of chemical intermediates and fine chemicals such as alcohols, amines, carboxylic acids, and the like.
At present, the key technical problem of synthesizing high added value aldehyde compounds by olefin hydroformylation is how to realize the regioselectivity of CO inserted into different positions of C=C bonds; the Co-based catalysts developed earlier have lower catalytic activity and aldehyde-based regioselectivity, and were later replaced by Rh-based phosphine complex catalysts (j.catalyst, 2021, 401, 321-330; new j.chem.,2020, 44, 20-23). From homogeneous catalysis to heterogeneous catalysis, rh-based catalysts are being intensively studied for the hydroformylation of olefins. The performance of the Rh-based catalysts can be achieved at 0.2 to 24.2 in terms of the selectivity ratio of linear aldehydes to branched aldehydes (j.catalyst., 2006, 243, 318-328; green chem.,2016, 18, 2995-3005.). However, due to the rapid increase in price of the international Rh metal, the corresponding process costs are increased, and therefore, it is necessary to develop other catalytic systems having comparable performance for hydroformylation.
Since Ir and Rh are in the same group, ir-based catalysts have the ability to catalyze olefin hydroformylation in theory, but the existing Ir-based catalysts have the following problems: (1) The catalytic hydroformylation is very low (chem. Eur. J.2022, 28, e 202104012; catalyst. Sci. Technology. 2016,6, 208-214; org. Biomol. Chem.2023, 21, 6410-6418; J. Catal.2019, 373, 215-221.), (2) from the results, the ratio of linear to branched aldehydes is greater than 1, the market also has a need for branched aldehydes such as isobutyraldehyde, and processes with a ratio of linear to branched aldehydes of less than 1 are also the industry pursuing. (3) Meanwhile, the existing Ir-based catalyst is mainly a homogeneous catalytic system, and the recoverable performance is poor.
Aiming at the problems, the invention develops a method for preparing aldehyde by using heterogeneous Ir-based catalyst in propylene hydroformylation. Compared with Rh-based catalyst, the process cost is reduced; compared with a homogeneous Ir-based catalyst, the recoverable performance is improved. In addition, the heterogeneous Ir-based catalyst has a linear aldehyde/branched aldehyde ratio of less than 1, excellent branched chain selectivity and catalytic reaction efficiency, and a highest catalyst conversion number (TON) of 21916, and has good industrial application prospect.
Disclosure of Invention
The first object of the present invention is to provide a heterogeneous Ir-based catalyst preparation method, which reduces the process cost compared with the Rh-based catalyst; compared with a homogeneous Ir-based catalyst, the recoverable performance is improved.
The second object of the present invention is to provide a process for acrolein treatment with an Ir-based catalyst, which has excellent reactivity against hydroformylation of propylene, has excellent branched product selectivity, and has a linear aldehyde/branched aldehyde ratio of less than 1.
The specific technical scheme of the invention is as follows:
the invention provides a heterogeneous Ir-based catalyst, which has a chemical structural formula as follows:
the Ir catalyst (p-TBCP-Ir) is obtained by a one-pot method, and a porous organic framework with an Ir center active site is constructed by coordination polymerization of zirconium Zr, triphenylphosphine and carboxyl functional group derivatives thereof. Wherein the phosphine ligand is a triphenylphosphine compound functionalized by carboxylic acid, and can be TBCP or TDBCP.
The invention also provides a preparation method of the Ir catalyst, which comprises the following steps:
firstly, preparing a triphenylphosphine compound functionalized by carboxylic acid, firstly reacting p-dibromobenzene, phosphorus trichloride and n-butyllithium in a nitrogen atmosphere, then blowing carbon dioxide into a reaction system, extracting bromine by using the n-butyllithium, and finally acidizing by hydrochloric acid to obtain TBCP; the second step is to synthesize phosphine ligands TBCP and Ir 2 cod 2 Cl 2 、ZrCl 4 And placing benzoic acid into DMF solution for one-pot hydrothermal polymerization, and finally obtaining the heterogeneous iridium-based catalyst p-TBCP-Ir. The synthesis of TDBCP can be achieved by 4, 4-dibromobiphenyl based on a similar method of synthesizing TBCP from dibromobenzene.
In the presence of the heterogeneous iridium-based catalyst, propylene, carbon monoxide and hydrogen are used as raw materials to carry out catalytic reaction, and the prepared catalyst is more favorable for the generation of branched products in the hydroformylation reaction, and the positive-to-negative ratio is less than 1, wherein the reaction formula is as follows:
drawings
Fig. 1 is a schematic structural diagram of a heterogeneous iridium-based catalyst provided by the invention.
FIG. 2 is a nuclear magnetic resonance spectrum of a phosphine ligand TBCP of the present invention
FIG. 3 is an electron microscope image of a heterogeneous catalyst according to the invention
Detailed description of the preferred embodiments
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1:
the preparation method of the heterogeneous iridium-based catalyst comprises the following steps:
synthesis of TBCP: n-butyllithium in hexane was added dropwise to p-dibromobenzene in dry tetrahydrofuran solution over 30 minutes under nitrogen atmosphere. Then, phosphorus trichloride dissolved in an anhydrous THF solution was added dropwise to the above suspension. The mixture was stirred and reacted for 2 hours until the system was slowly warmed to ambient temperature. Subsequently, n-butyllithium was added over 30 minutes, and after stirring for 4 hours, dry carbon dioxide was introduced into the reaction mixture until the reaction solution became white. Finally, the pH was adjusted to about 1.0 with dilute hydrochloric acid, washed with water to ph=7, and dried under vacuum to obtain a white powder product (TBCP) in 65% yield.
Example 2:
synthesis of p-TBCP-Ir: TBCP and Ir 2 cod 2 Cl 2 At ambient temperatureStirring in THF solution for 2 hours, then removing the solvent under vacuum to obtain the catalyst monomer; subsequently, zrCl is added 4 Adding benzoic acid and N, N-Dimethylformamide (DMF) into a pressure-resistant container, and performing hydrothermal polymerization reaction for 24 hours at the temperature of 100 ℃; finally, the heterogeneous iridium catalyst p-TBCP-Ir in the form of pale yellow powder can be obtained, and the yield is 70 percent.
Example 3:
synthesis of TDBCP: n-butyllithium in hexane was added dropwise to 4, 4-dibromobiphenyl in dry tetrahydrofuran solution over 30 minutes under nitrogen atmosphere. Then, phosphorus trichloride dissolved in an anhydrous THF solution was added dropwise to the above suspension. The mixture was stirred and reacted for 2 hours until the system was slowly warmed to ambient temperature. Subsequently, n-butyllithium was added over 30 minutes, and after stirring for 4 hours, dry carbon dioxide was introduced into the reaction mixture until the reaction solution became white. Finally, the pH was adjusted to about 1.0 with dilute hydrochloric acid, washed with water to ph=7, and dried under vacuum to obtain a white powder product (TDBCP) in 70% yield.
Example 4:
synthesis of p-TDBCP-Ir: the specific procedure was the same as in example 2. TDBCP and Ir 2 cod 2 Cl 2 Stirring in THF solution at ambient temperature for 2 hours, then removing the solvent under vacuum to obtain the catalyst monomer; subsequently, zrCl is added 4 Adding benzoic acid and N, N-Dimethylformamide (DMF) into a pressure-resistant container, and performing hydrothermal polymerization reaction for 24 hours at the temperature of 100 ℃; finally, the heterogeneous iridium catalyst p-TBCP-Ir in the form of pale yellow powder can be obtained, and the yield is 75 percent.
Example 5:
the hydroformylation reaction is operated as follows:
in a 50mL high pressure stainless steel reactor equipped with magnetic stirring and heating, 5mg of heterogeneous Ir catalyst p-TBCP-Ir and 5mL of solvent toluene were added. Then, propylene 8bar, carbon monoxide 15bar and hydrogen 15bar were filled into the autoclave, respectively, and reacted for 16 hours. After the reaction, the catalyst was separated by centrifugation and the supernatant was detected by gas chromatography analysis and TON was calculated using n-butyl acetate as an internal standard. According to the gas phase result, the catalyst conversion number TON can reach 21916, and the selectivity of the n-butyraldehyde and the iso-butyraldehyde is 99 percent (n-butyraldehyde/iso-butyraldehyde=0.6.
Example 6:
the hydroformylation reaction is operated as follows:
in a 50mL high pressure stainless steel reactor equipped with magnetic stirring and heating, 5mg of heterogeneous Ir catalyst p-TDBCP-Ir and 5mL of solvent toluene were added. Then, propylene 8bar, carbon monoxide 15bar and hydrogen 15bar were filled into the autoclave, respectively, and reacted for 16 hours. After the reaction, the catalyst was separated by centrifugation and the supernatant was detected by gas chromatography analysis and TON was calculated using n-butyl acetate as an internal standard. According to the gas phase result, the catalyst conversion number TON can reach 17421, and the selectivity of n-butyraldehyde and iso-butyraldehyde is 99% (n-butyraldehyde/iso-butyraldehyde=0.6.
Examples 7 to 10:
the influence method of different temperatures on the hydroformylation reaction of propylene is explored, and the results are shown in table 1:
TABLE 1 influence of temperature on the hydroformylation of propylene
| Examples | Temperature (. Degree. C.) | Catalyst conversion number (TON) | N-isobutyraldehyde selectivity (%) | N-butyraldehyde/iso-butyraldehyde (n/i) |
| 7 | 80 | 2669 | 99 | 0.88 |
| 8 | 100 | 21916 | 99 | 0.62 |
| 9 | 120 | 16103 | 99 | 0.63 |
| 10 | 140 | 12560 | 99 | 0.7 |
Examples 11 to 16:
the effect method of different solvents on the hydroformylation reaction of propylene is explored, and the results are shown in table 2:
TABLE 1 influence of different solvents on the hydroformylation of propylene
| Examples | Solvent(s) | Catalyst conversion number (TON) | N-isobutyraldehyde selectivity (%) | N-butyraldehyde/iso-butyraldehyde (n/i) |
| 11 | Acetonitrile | 14130 | 99 | 0.78 |
| 12 | N-methylpyrrolidone | 4637 | 99 | 1.13 |
| 13 | Toluene (toluene) | 21916 | 99 | 0.62 |
| 14 | N, N-dimethylformamide | 2777 | 99 | 1 |
| 15 | Dioxahexacyclic ring | 20531 | 99 | 0.7 |
| 16 | Dimethyl sulfoxide | 4691 | 99 | 1.3 |
From the above table, it can be seen that the hydroformylation reaction is best at a temperature of 100 ℃ in the hydroformylation reaction process by adopting the heterogeneous iridium-based catalyst of the invention, and the n-butyraldehyde/isobutyraldehyde ratio of 0.6 is obtained, which means that the catalyst of the invention has better production efficiency of branched aldehyde, high catalytic efficiency and certain industrial application prospect.
Claims (7)
1. The heterogeneous iridium-based catalyst is characterized in that the Ir catalyst (p-TBCP-Ir) is obtained by a one-pot method, a porous organic framework with an Ir center active site is constructed by coordination polymerization of zirconium Zr, triphenylphosphine and carboxyl functional group derivatives thereof, and the iridium-based catalyst has a chemical structural formula as follows:
wherein the phosphine ligand is a triphenylphosphine compound functionalized by carboxylic acid, and can be TBCP or TDBCP.
2. The iridium-based catalyst structure according to claim 1, characterized by comprising the following preparation steps: firstly, preparing a triphenylphosphine compound functionalized by carboxylic acid, firstly reacting p-dibromobenzene, phosphorus trichloride and n-butyllithium in a nitrogen atmosphere, then blowing carbon dioxide into a reaction system, extracting bromine by using the n-butyllithium, and finally acidizing by hydrochloric acid to obtain TBCP; the second step is to synthesize phosphine ligands TBCP and Ir 2 cod 2 Cl 2 、ZrCl 4 And placing benzoic acid into DMF solution for one-pot hydrothermal polymerization to finally obtain the heterogeneous base catalyst p-TBCP-Ir.
3. The preparation method according to claim 2, characterized in that in the preparation of the carboxylic acid functionalized triphenylphosphine compound, the synthesis of TDBCP can be achieved by 4, 4-dibromobiphenyl based on a similar method for synthesizing TBCP from dibromobenzene.
4. The preparation method according to claim 2, wherein the required reaction temperature is from-70 to 40 ℃ and then stirring is carried out for 1.5 to 6 hours; the reaction temperature required by the one-pot method for preparing the heterogeneous iridium-based catalyst p-TBCP-Ir is 60-120 ℃ and the reaction lasts for 8-24 hours.
5. A process for acrolein treatment using a heterogeneous catalyst prepared according to claim 1 or any one of claims 2 to 4, characterized by comprising the steps of: in the presence of the heterogeneous iridium-based catalyst, propylene, carbon monoxide and hydrogen are used as raw materials to carry out catalytic reaction, wherein the reaction formula is shown as follows:
6. the process of claim 5 wherein the catalyst prepared is more conducive to the formation of branched products in the hydroformylation reaction with an n-to-iso ratio of less than 1.
7. The method according to claim 5, wherein the reaction temperature of the catalytic reaction is 70-130 ℃; the reaction pressure is 0.5-3.0 MPa; the partial pressure ratio of propylene to the carbon monoxide is 10:1-1:10; the partial pressure ratio of propylene to hydrogen is 10:1-1:10; wherein the mass of the catalyst is 0.005-5.0wt% of the mass of the solvent.
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