CN115521194A - Method for regulating catalytic performance of catalyst based on anion-pi action - Google Patents
Method for regulating catalytic performance of catalyst based on anion-pi action Download PDFInfo
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- CN115521194A CN115521194A CN202211362105.2A CN202211362105A CN115521194A CN 115521194 A CN115521194 A CN 115521194A CN 202211362105 A CN202211362105 A CN 202211362105A CN 115521194 A CN115521194 A CN 115521194A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 43
- 150000001336 alkenes Chemical class 0.000 claims abstract description 41
- 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
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 230000000694 effects Effects 0.000 claims abstract description 16
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 16
- 230000001276 controlling effect Effects 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 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
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 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
- 238000004817 gas chromatography Methods 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000011261 inert gas Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 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
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
Classifications
-
- 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 catalytic performance of a catalyst based on anion-pi action, which relates to the technical field of organic synthesis and sequentially comprises the following steps: (1) Mixing olefin, rhodium precursor, phosphine ligand and organic solvent, charging CO and H 2 The synthesis gas is subjected to homogeneous reaction at the temperature of between 30 and 140 ℃, after the reaction is finished, unreacted olefin and newly generated aldehyde are removed, and then new olefin is added; adding anions, and carrying out homogeneous reaction at the temperature of 30-140 ℃ until the reaction is stopped; adding cation, and carrying out homogeneous reaction at 30-140 deg.CThe reaction is restarted. According to the invention, through adding anions and cations, the performance of the catalyst is adjusted, so that the reaction is suspended or started, and the effect of switching is achieved. 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 catalytic performance of a catalyst based on anion-pi action.
Background
The catalyst conforms to the principle of green chemistry, has the characteristics of high activity, good selectivity and mild catalytic conditions, and is an ideal choice, at present, under the inspiration of natural enzymes, an intelligent technology responding to microenvironment change and a switchable catalytic technology become research hotspots in the field of catalysis, the activity or selectivity of a single catalyst can be regulated and controlled by external stimuli, including chemistry, electricity, heat and light, however, the activity or selectivity of the single catalyst can be usually regulated and controlled by elaborately designing molecules with specific stimuli-responding functional groups, and therefore, a simple catalyst regulation and control method is urgently needed to be searched.
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 effect 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 anion-pi action sequentially comprises the following steps of:
(1) Mixing olefin, rhodium precursor, phosphine ligand and organic solvent, charging CO and H 2 The synthesis gas is subjected to homogeneous reaction at the temperature of between 30 and 140 ℃, after the reaction is finished, unreacted olefin and newly generated aldehyde are removed, and then new olefin is added;
(2) Adding anions, and carrying out homogeneous reaction at 30-140 ℃ until the reaction is stopped;
(3) Adding cation, homogeneous reaction at 30-140 deg.c and re-starting the reaction.
The invention has the beneficial effects that: the phosphine ligand is provided with an electron-withdrawing group, so that an aromatic ring of the phosphine ligand is electron-deficient, the added anion is electron-rich, the phosphine ligand and the anion generate electrostatic action, also can be called anion-pi action, the anion refers to the subsequently added anion, and the pi refers to the aromatic ring with the electron-withdrawing group, so that the activity of the catalyst 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.
On the basis of the technical scheme, the invention can be further improved as follows:
further, in step (1), the molar ratio of the olefin, the rhodium precursor and the 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 olefin having an aromatic ring.
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 (ii) a Wherein acac is acetylacetone, cod is 1,4-cyclooctadiene, and Cp is pentamethylcyclopentadiene.
Further, in the 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, dichloromethane, chloroform, mixed alkane and acetonitrile.
Further, in the step (1), the molar volume ratio of the olefin to the organic solvent is 4-6mmol:3mL.
Further, in the step (1), the pressure of the synthesis gas is 1-6MPa.
Further, in step (1), CO and H 2 In a volume ratio of 1-3:1-3.
Further, in the step (1), carrying out homogeneous reaction for 4-8h at the temperature of 30-140 ℃.
Further, in the step (1), the homogeneous reaction is carried out for 5-8h at the temperature of 40-80 ℃.
Further, in the step (2), the anion is F - 、Cl - 、Br - 、I - 、HSO 4 - Or NO 3 - 。
Further, in the step (2), the molar ratio of the anion to the olefin is 0.003-0.06:1.
further, in the step (2), the homogeneous reaction is carried out for 2.5 to 3.5 hours at the temperature of between 30 and 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 the step (3), the molar ratio of the cation to the anion is 1.2-1:1.
further, in the step (3), the molar ratio of the cation to the anion is 1:1.
further, in the step (3), the homogeneous reaction is carried out for 4 to 8 hours at the temperature of between 30 and 140 ℃.
Further, in the step (3), the homogeneous reaction is carried out for 5 to 8 hours at the temperature of between 40 and 80 ℃.
The invention has the following beneficial effects:
1. according to the invention, through adding anions and cations, the performance of the catalyst is adjusted, so that the reaction is suspended or started, and the effect of switching is achieved.
2. The method can well regulate and control the reaction to achieve the aim of suspending or starting, the catalyst can be recycled in the whole reaction, meanwhile, the reaction temperature is low, the production energy consumption is reduced, the pressure of the synthesis gas 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 this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1:
a method for regulating and controlling catalytic performance of a catalyst based on anion-pi action sequentially comprises the following steps:
(1) 5mmol of styrene, 0.01mmol of the rhodium precursor Rh (acac) (CO) 2 0.03mmol of phosphine ligand L4 and 3mL of organic solvent toluene are mixed and placed in a high-pressure reaction kettle with magnetic stirring, inert gas replaces the air in the kettle, and 3MPa of synthetic gas (CO and H) is filled 2 Is 2: 1) Carrying out homogeneous reaction for 8h at 40 ℃, removing unreacted olefin and newly generated aldehyde after the reaction is finished, and then adding 5mmol of styrene;
(2) Adding 0.05mmol of anion F-, sealing, carrying out homogeneous reaction for 3h at 40 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) Adding 0.05mmol of cation [ NO ]] + And sealing, carrying out homogeneous reaction for 8h 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 catalytic performance of a catalyst based on anion-pi action sequentially comprises the following steps:
(1) 6mmol of cyclohexene, 0.018mmol of the rhodium precursor Rh (acac) (CO) 2 0.048mmol of phosphine ligand L1 and organic solvent anisole are mixed and put into a high-pressure reaction kettle with magnetic stirring, inert gas replaces the air in the kettle, and 4MPa of synthesis gas (CO and H) is filled 2 Is 2: 1) Carrying out homogeneous reaction for 5h at the temperature of 80 ℃, removing unreacted olefin and newly generated aldehyde after the reaction is finished, and then adding 6mmol of cyclohexene;
(2) 0.018mmol of anion F was added - Sealing, carrying out homogeneous reaction for 3h at 80 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) Adding 0.0018mmol of cation Ag + The reaction is restarted and sealed, the homogeneous reaction is carried out for 5h at the temperature of 80 ℃, and the conversion rate of olefin and the yield of aldehyde are detected by gas chromatography, so that the reaction is restarted. The reaction equation is as follows:
example 3:
a method for regulating and controlling catalytic performance of a catalyst based on anion-pi action sequentially comprises the following steps:
(1) 4mmol of styrene, 0.004mmol of the rhodium precursor Rh (acac) (CO) 2 0.012mmol of phosphine ligand L2 and organic solvent n-hexane, placing in a high-pressure reaction kettle with magnetic stirring, replacing the air in the kettle with inert gas, and charging 2MPa of synthesis gas (CO and H) 2 Is 1: 1) Carrying out homogeneous reaction for 7h at 70 ℃, removing unreacted olefin and newly generated aldehyde after the reaction is finished, and then adding 4mmol of styrene;
(2) Adding 0.24mmol anion Br-, sealing, carrying out homogeneous reaction for 3h at 70 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) Adding 0.24mmol of cation Ag + And sealing, carrying out homogeneous reaction for 7h at 70 ℃, 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 4:
a method for regulating and controlling catalytic performance of a catalyst based on anion-pi action sequentially comprises the following steps:
(1) 5mmol of octene, 0.015mmol of rhodium precursor Rh (acac) (CO) 2 0.03mmol of phosphine ligand L2 and organic solvent xylene, placing the mixture in a high-pressure reaction kettle with magnetic stirring, replacing the air in the kettle with inert gas, and filling 1MPa of synthetic gas (CO and H) 2 Is 1: 2) Carrying out homogeneous reaction for 8h at 40 ℃, removing unreacted olefin and newly generated aldehyde after the reaction is finished, and then adding 5mmol of octene;
(2) Adding 0.05mmol of anion I-, sealing, carrying out homogeneous reaction for 3h at 40 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) Adding 0.05mmol of cation Ag + And sealing, carrying out homogeneous reaction for 8h 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 catalytic performance of a catalyst based on anion-pi action sequentially comprises the following steps:
(1) 5mmol of 2-pentene and 0.015mmol of the rhodium precursor Rh (acac) (CO) 2 0.06mmol of phosphine ligand L4 and organic solvent trimethylbenzene are mixed and put into a high-pressure reaction kettle with magnetic stirring, inert gas replaces the air in the kettle, and 2MPa of synthetic gas (CO and H) is filled 2 Is 1: 1) Carrying out homogeneous reaction for 6h at the temperature of 60 ℃, removing unreacted olefin and newly generated aldehyde after the reaction is finished, and then adding 5mmol of 2-pentene;
(2) 0.05mmol of anion F was added - Sealing, carrying out homogeneous reaction for 3h at 60 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) Adding 0.05mmol of cation K + And sealing, carrying out homogeneous reaction for 6h at the temperature of 60 ℃, 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 6:
a method for regulating and controlling catalytic performance of a catalyst based on anion-pi action sequentially comprises the following steps:
(1) 5mmol of styrene, 0.02mmol of the rhodium precursor Rh (acac) (CO) 2 0.04mmol of phosphine ligand L2 and organic solvent trimethylbenzene are mixed and put into a high-pressure reaction kettle with magnetic stirring, inert gas replaces the air in the kettle, and 6MPa of synthesis gas (CO and H) is filled 2 Is 1: 2) Carrying out homogeneous reaction for 6h at 70 ℃, removing unreacted olefin and newly generated aldehyde after the reaction is finished, and then adding 5mmol of styrene;
(2) 0.05mmol of anion F was added - Sealing, carrying out homogeneous reaction for 3h at 70 ℃, detecting the conversion rate of olefin and the yield of aldehyde by using gas chromatography, and finding that the reaction is stopped;
(3) Adding 0.05mmol of cation Ag + And sealing, carrying out homogeneous reaction for 6h at 70 ℃, 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:
test examples
1. After the reaction in step (1) of examples 1 to 6 is finished, adding a new reaction solution before the olefin, the reaction solution in step (2) and the reaction solution in step (3), respectively, and detecting the content of the product, wherein the detection method specifically adopts gas chromatography, and the yield of the product aldehyde is calculated, and the result is shown in table 1.
As can be seen from Table 1, the reaction is almost stopped when the anion is added into the reaction system, and the reaction is restarted after the cation is added, which shows that the method of the invention can regulate the catalytic stop and start of the catalyst.
TABLE 1 yield of product aldehyde
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.
Claims (10)
1. A method for regulating and controlling catalytic performance of a catalyst based on anion-pi action is characterized by sequentially comprising the following steps:
(1) Mixing olefin, rhodium precursor, phosphine ligand and organic solvent, charging CO and H 2 The synthesis gas is subjected to homogeneous reaction at the temperature of between 30 and 140 ℃, after the reaction is finished, unreacted olefin and newly generated aldehyde are removed, and then new olefin is added;
(2) Adding anions, and carrying out homogeneous reaction at the temperature of 30-140 ℃ until the reaction is stopped;
(3) Adding cation, and homogenizing at 30-140 deg.C to restart reaction.
2. The method for regulating the catalytic performance of the catalyst based on anion-pi effect according to claim 1, wherein in the step (1), the molar ratio of the olefin, the rhodium precursor and the phosphine ligand is 1:0.001-0.004:0.003-0.012.
3. The method for regulating and controlling the catalytic performance of a catalyst based on the anion-pi effect as claimed in claim 1 or 2, wherein in the step (1), the olefin is a linear olefin, a cyclic olefin, an internal olefin or an olefin with an aromatic ring.
4. The method for regulating the catalytic performance of a catalyst based on anion-pi action according to claim 1 or 2, wherein 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 (ii) a Wherein acac is acetylacetone, cod is 1,4-cyclooctadiene, and Cp is pentamethylcyclopentadiene.
5. The method for regulating the catalytic performance of a catalyst based on anion-pi effect according to claim 1 or 2, wherein in the step (1), the phosphine ligand is
6. The method for regulating and controlling the catalytic performance of the catalyst based on the anion-pi effect according to claim 1 or 2, 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, dichloromethane, chloroform, mixed alkanes and acetonitrile.
7. The method for regulating the catalytic performance of a catalyst based on anion-pi effect as claimed in claim 1, wherein in the step (2), the anion is F - 、Cl - 、Br - 、I - 、HSO 4 - Or NO 3 - 。
8. The method for regulating the catalytic performance of a catalyst based on the anion-pi effect according to claim 1, wherein in the step (2), the molar ratio of the anion to the olefin is 0.003-0.06:1.
9. the method for regulating the catalytic performance of a catalyst based on anion-pi effect as claimed in claim 1, wherein in the step (3), the cation is Ag + And/or [ NO] + 。
10. The method for regulating the catalytic performance of a catalyst based on anion-pi effect according to claim 1, wherein in the step (3), the molar ratio of the cation to the anion is 1.2-1:1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| 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 |
| CN109490291A (en) * | 2018-11-20 | 2019-03-19 | 上海应用技术大学 | Purposes of the 1,8- naphthoyl imide compounds based on electron-withdrawing group substitution as the colour reagent of fluorine ion |
| 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 |
-
2022
- 2022-11-02 CN CN202211362105.2A patent/CN115521194B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| 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 |
| CN109490291A (en) * | 2018-11-20 | 2019-03-19 | 上海应用技术大学 | Purposes of the 1,8- naphthoyl imide compounds based on electron-withdrawing group substitution as the colour reagent of fluorine ion |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| XIAONAN KANDENG: "Anion-π_interactions:from concept to application", CHINESE CHEMICAL LETTERS, vol. 29, pages 261 - 266 * |
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