CN115521194B - Method for regulating and controlling catalytic performance of catalyst based on anion-pi action - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 23
- 230000001276 controlling effect Effects 0.000 title claims abstract description 18
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 150000001336 alkenes Chemical class 0.000 claims abstract description 41
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 40
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001450 anions Chemical class 0.000 claims abstract description 24
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 23
- 239000010948 rhodium Substances 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 16
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 13
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- DNZZPKYSGRTNGK-PQZOIKATSA-N (1z,4z)-cycloocta-1,4-diene Chemical compound C1C\C=C/C\C=C/C1 DNZZPKYSGRTNGK-PQZOIKATSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- -1 cyclic olefin Chemical class 0.000 claims description 2
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004817 gas chromatography Methods 0.000 description 13
- 238000007789 sealing Methods 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 4
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
Classifications
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- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for regulating and controlling the catalytic performance of a catalyst based on an action of an anion-pi, which relates to the technical field of organic synthesis, and comprises the following steps in sequence: (1) Mixing olefin, rhodium precursor, phosphine ligand and organic solvent, and charging CO and H 2 Homogeneously reacting at 30-140 ℃, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding new olefin; adding anions, and carrying out homogeneous reaction at 30-140 ℃ until the reaction is stopped; adding cation, homogeneously reacting at 30-140 deg.c, and restarting. The invention adjusts the performance of the catalyst by adding anions and cations, so that the reaction is suspended or started, the effect of switching on and off is achieved, and the whole reaction is simple, convenient and easy to operate. The invention solves the problem of complex method for adjusting the performance of the catalyst in the prior art.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for regulating and controlling the catalytic performance of a catalyst based on an anion-pi effect.
Background
The catalyst accords with the green chemistry principle, has the characteristics of high activity, good selectivity and mild catalytic conditions, is an ideal choice, at present, under the inspired of natural enzymes, intelligent technology responding to micro-environment change and switchable catalytic technology become research hot spots in the catalytic field, and the activity or the selectivity of a single catalyst can be regulated and controlled by external stimulus, including chemistry, electricity, heat and light, however, the molecular with specific stimulus response functional groups usually needs to be carefully designed, so that a simple catalyst regulation method is urgently required to be sought.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a method for regulating and controlling the catalytic performance of a catalyst based on an anion-pi action, so as to solve the problem that the method for regulating the catalytic performance of the catalyst in the prior art is complex.
The technical scheme for solving the technical problems is as follows: the method for regulating and controlling the catalytic performance of the catalyst based on the action of an anion-pi comprises the following steps in sequence:
(1) Mixing olefin, rhodium precursor, phosphine ligand and organic solvent, and charging CO and H 2 Homogeneously reacting at 30-140 ℃, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding new olefin;
(2) Adding anions, and carrying out homogeneous reaction at 30-140 ℃ until the reaction is stopped;
(3) Adding cation, homogeneously reacting at 30-140 deg.c, and restarting.
The beneficial effects of the invention are as follows: because the phosphine ligand has electron-withdrawing groups, the phosphine ligand aromatic ring presents electron-deficient, the added anions present electron-rich shapes, the phosphine ligand and the anions generate electrostatic action, which can be also called an anion-pi action, wherein anion refers to the anions added subsequently, pi refers to the aromatic ring with electron-withdrawing groups, so that the catalyst activity is regulated and controlled, and the reaction is stopped; when the cation is added again, the cation consumes the anion, thereby restoring the catalyst activity and thus starting the reaction.
Based on the technical scheme, the invention can also be improved as follows:
further, in step (1), the molar ratio of olefin, rhodium precursor and phosphine ligand is 1:0.001-0.004:0.003-0.012.
Further, in the step (1), the olefin is a linear olefin, a cyclic olefin, an internal olefin, or an aromatic ring-carrying olefin.
Further, in the step (1), the rhodium precursor is Rh (acac) (CH 2 ＝CH 2 ) 2 、[RhCl(CH 2 ＝CH 2 ) 2 ] 2 、 Rh(cod) 2 BF 4 、HRh(CO)(TPP) 3 、[Rh(cod)Cl] 2 、[Rh(Cp*)Cl 2 ] 2 、RhCl 3 Or Rh (acac) (CO) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein acac is acetylacetone, cod is 1, 4-cyclooctadiene, and Cp is pentamethyl cyclopentadiene.
Further, in step (1), the phosphine ligand is
Further, in the step (1), the organic solvent is at least one of anisole, toluene, n-hexane, diethyl ether, tetrahydrofuran, xylene, trimethylbenzene, 1, 4-dioxane, methylene chloride, chloroform, mixed alkane and acetonitrile.
Further, in the step (1), the molar volume ratio of the olefin to the organic solvent is 4 to 6mmol:3mL.
Further, in the step (1), the pressure of the synthesis gas is 1-6MPa.
Further, in step (1), CO and H 2 The volume ratio of (2) is 1-3:1-3.
Further, in the step (1), the homogeneous reaction is carried out for 4 to 8 hours at the temperature of 30 to 140 ℃.
Further, in the step (1), the homogeneous reaction is carried out for 5 to 8 hours at the temperature of 40 to 80 ℃.
Further, in step (2), the anion is F - 、Cl - 、Br - 、I - 、HSO 4 - Or NO 3 - 。
Further, in step (2), the molar ratio of anions to olefins is from 0.003 to 0.06:1.
further, in the step (2), the homogeneous reaction is carried out for 2.5 to 3.5 hours at the temperature of 30 to 140 ℃.
Further, in the step (2), the homogeneous reaction is carried out for 3 hours at the temperature of 40-80 ℃.
Further, in the step (3), the cation is Ag + And/or [ NO ]] + 。
Further, in step (3), the molar ratio of cations to anions is 1.2 to 1:1.
further, in step (3), the molar ratio of cations to anions is 1:1.
further, in the step (3), the homogeneous reaction is carried out for 4 to 8 hours at the temperature of 30 to 140 ℃.
Further, in the step (3), the homogeneous reaction is carried out for 5 to 8 hours at the temperature of 40 to 80 ℃.
The invention has the following beneficial effects:
1. the invention adjusts the performance of the catalyst by adding anions and cations, so that the reaction is suspended or started, the effect of switching on and off is achieved, and the whole reaction is simple, convenient and easy to operate.
2. The method can well regulate and control the reaction to achieve the aim of stopping or starting, the whole reaction can be recycled, meanwhile, the reaction temperature is low, the production energy consumption is reduced, the synthesis gas pressure is low and stable, the production safety is improved, the consumption of the catalyst and the ligand is low, and the production cost is reduced.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the 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:
a method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi comprises the following steps in sequence:
(1) 5mmol of styrene0.01mmol rhodium precursor Rh (acac) (CO) 2 Mixing 0.03mmol phosphine ligand L4 with 3mL toluene, placing in a magnetically stirred high-pressure reactor, replacing air in the reactor with inert gas, and charging 3MPa synthesis gas (CO and H) 2 The volume ratio of (2): 1) Homogeneously reacting for 8 hours at 40 ℃, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding 5mmol of styrene;
(2) Adding 0.05mmol of anion F-, sealing, carrying out homogeneous reaction at 40 ℃ for 3 hours, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) 0.05mmol of cation [ NO ] is added] + Sealing, carrying out homogeneous reaction for 8 hours at 40 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is restarted. The reaction equation is as follows:
example 2:
a method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi comprises the following steps in sequence:
(1) 6mmol cyclohexene, 0.018mmol rhodium precursor Rh (acac) (CO) 2 Mixing phosphine ligand L1 of 0.048mmol with anisole as organic solvent, placing in a magnetically stirred high-pressure reactor, replacing air in the reactor with inert gas, and charging 4MPa of synthesis gas (CO and H) 2 The volume ratio of (2): 1) Homogeneously reacting for 5 hours at 80 ℃, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding 6mmol cyclohexene;
(2) 0.018mmol of anion F was added - Sealing, carrying out homogeneous reaction for 3 hours at 80 ℃, and detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography to find that the reaction is stopped;
(3) 0.0018mmol of cationic Ag is added + The reaction was restarted, sealed, and the homogeneous reaction was carried out at 80℃for 5 hours, and the conversion of olefins and the yield of aldehydes were detected by gas chromatography, and the restart of the reaction was found. Equation of reactionThe formula is as follows:
example 3:
a method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi comprises the following steps in sequence:
(1) 4mmol of styrene, 0.004mmol of rhodium precursor Rh (acac) (CO) 2 Mixing phosphine ligand L2 in 0.012mmol with n-hexane, placing in a magnetically stirred high-pressure reactor, replacing air in the reactor with inert gas, and charging 2MPa of synthesis gas (CO and H) 2 The volume ratio of (1): 1) Homogeneously reacting at 70 ℃ for 7 hours, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding 4mmol of styrene;
(2) Adding 0.24mmol of anion Br-, sealing, carrying out homogeneous reaction for 3 hours at 70 ℃, and detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography to find that the reaction is stopped;
(3) 0.24mmol of cationic Ag is added + Sealing, carrying out homogeneous reaction for 7h at 70 ℃, detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography, and finding that the reaction is restarted. The reaction equation is as follows:
example 4:
a method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi comprises the following steps in sequence:
(1) 5mmol octene, 0.015mmol rhodium precursor Rh (acac) (CO) 2 Mixing phosphine ligand L2 of 0.03mmol with organic solvent xylene, placing in a high-pressure reaction kettle with magnetic stirring, replacing air in the kettle with inert gas, and charging 1MPa of synthesis gas (CO and H) 2 The volume ratio of (1): 2) Homogeneously reacting for 8 hours at 40 ℃, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding 5mmol of octene;
(2) Adding 0.05mmol of anion I-, sealing, carrying out homogeneous reaction at 40 ℃ for 3 hours, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) 0.05mmol of cationic Ag is added + Sealing, carrying out homogeneous reaction for 8 hours at 40 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is restarted. The reaction equation is as follows:
example 5:
a method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi comprises the following steps in sequence:
(1) 5mmol of 2-pentene, 0.015mmol of rhodium precursor Rh (acac) (CO) 2 Mixing phosphine ligand L4 of 0.06mmol with trimethylbenzene as organic solvent, placing in a high-pressure reaction kettle with magnetic stirring, replacing air in the kettle with inert gas, and charging 2MPa of synthesis gas (CO and H) 2 The volume ratio of (1): 1) Homogeneously reacting at 60 ℃ for 6 hours, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding 5mmol of 2-pentene;
(2) 0.05mmol of anion F is added - Sealing, carrying out homogeneous reaction for 3 hours at 60 ℃, and detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography to find that the reaction is stopped;
(3) 0.05mmol of cation K is added + Sealing, carrying out homogeneous reaction for 6h at 60 ℃, detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography, and finding out that the reaction is restarted. The reaction equation is as follows:
example 6:
a method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi comprises the following steps in sequence:
(1) 5mmol of styrene and 0.02mmol of rhodium were addedBody Rh (acac) (CO) 2 Mixing phosphine ligand L2 of 0.04mmol with trimethylbenzene as organic solvent, placing in a magnetically stirred high-pressure reactor, replacing air in the reactor with inert gas, and charging 6MPa of synthesis gas (CO and H) 2 The volume ratio of (1): 2) Homogeneously reacting at 70 ℃ for 6 hours, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding 5mmol of styrene;
(2) 0.05mmol of anion F is added - Sealing, carrying out homogeneous reaction for 3 hours at 70 ℃, and detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography to find that the reaction is stopped;
(3) 0.05mmol of cationic Ag is added + Sealing, carrying out homogeneous reaction for 6h at 70 ℃, detecting the conversion rate of olefin and the yield of aldehyde by utilizing gas chromatography, and finding out that the reaction is restarted. The reaction equation is as follows:
test examples
1. After the reaction of the step (1) in examples 1 to 6 was completed, a new reaction solution before olefin was added, a reaction solution in the step (2) and a reaction solution in the step (3) were respectively added to carry out the detection of the product content, specifically, by using gas chromatography, and the yield of the product aldehyde was calculated, and the results are shown in Table 1.
As can be seen from Table 1, the addition of anions to the reaction system almost stopped, and the reaction was restarted after the addition of cations, demonstrating that the method of the present invention was able to regulate the catalytic stopping and starting of the catalyst.
TABLE 1 yield of product aldehyde
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (6)
1. A method for regulating and controlling the catalytic performance of a catalyst based on an action of an ion-pi is characterized by sequentially comprising the following steps:
(1) Mixing olefin, rhodium precursor, phosphine ligand and organic solvent, and charging CO and H 2 Homogeneously reacting at 30-140 ℃, removing unreacted olefin and new aldehyde after the reaction is finished, and then adding new olefin;
(2) Adding anions, and carrying out homogeneous reaction at 30-140 ℃ until the reaction is stopped;
(3) Adding cations, carrying out homogeneous reaction at 30-140 ℃, and restarting the reaction;
in step (1), the rhodium precursor is Rh (acac) (CH 2 =CH 2 ) 2 、[RhCl(CH 2 =CH 2 ) 2 ] 2 、Rh(cod) 2 BF 4 、HRh(CO)(TPP) 3 、[Rh(cod)Cl] 2 、[Rh(Cp*)Cl 2 ] 2 、RhCl 3 Or Rh (acac) (CO) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein acac is acetylacetone, cod is 1, 4-cyclooctadiene, and Cp is pentamethyl cyclopentadiene;
in step (1), the phosphine ligand is、/>、/>Or (b)；
In the step (2), the anion is F - 、Cl - 、Br - 、I - 、HSO 4 - Or NO 3 - ；
In the step (3), the cation is Ag + And/or [ NO ]] + 。
2. The method for controlling the catalytic performance of a catalyst based on an action of an anion-pi according to claim 1, wherein in step (1), the molar ratio of olefin, rhodium precursor and phosphine ligand is 1:0.001-0.004:0.003-0.012.
3. The method for controlling the catalytic performance of a catalyst based on an action of an ion-pi according to claim 1 or 2, wherein in the step (1), the olefin is a linear olefin, a cyclic olefin, an internal olefin, or an aromatic ring-carrying olefin.
4. The method for controlling the catalytic performance of a catalyst based on an action of an anion-pi according to claim 1, wherein in the step (1), the organic solvent is at least one of anisole, toluene, n-hexane, diethyl ether, tetrahydrofuran, xylene, trimethylbenzene, 1, 4-dioxane, methylene chloride, chloroform, mixed alkane and acetonitrile.
5. The method for controlling the catalytic performance of a catalyst based on an action of an anion-pi according to claim 1, wherein in the step (2), the molar ratio of anions to olefins is 0.003 to 0.06:1.
6. the method for controlling the catalytic performance of a catalyst based on an action of an anion-pi according to claim 1, wherein in step (3), the molar ratio of cations to anions is 1.2 to 1:1.
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| CN105669403A (en) * | 2016-03-19 | 2016-06-15 | 青岛科技大学 | Method of preparing normal aldehyde in highly selective manner through olefin two-phase hydroformylation on basis of phosphine functionalized polyether pyrrolidine salt ion liquid |
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| CN113351249A (en) * | 2021-04-29 | 2021-09-07 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
| CN115254195A (en) * | 2022-07-29 | 2022-11-01 | 迈瑞尔实验设备（上海）有限公司 | Catalytic system for olefin hydroformylation reaction |
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| CN113351249A (en) * | 2021-04-29 | 2021-09-07 | 四川大学 | Catalytic system for preparing aldehyde by catalyzing hydroformylation of internal olefin |
| CN115254195A (en) * | 2022-07-29 | 2022-11-01 | 迈瑞尔实验设备（上海）有限公司 | Catalytic system for olefin hydroformylation reaction |
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