CN114591373A - Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium - Google Patents
Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium Download PDFInfo
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- CN114591373A CN114591373A CN202210262699.3A CN202210262699A CN114591373A CN 114591373 A CN114591373 A CN 114591373A CN 202210262699 A CN202210262699 A CN 202210262699A CN 114591373 A CN114591373 A CN 114591373A
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- rhodium
- acetylacetonatocarbonyltriphenylphosphine
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- 239000010948 rhodium Substances 0.000 title claims abstract description 85
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010992 reflux Methods 0.000 claims abstract description 43
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012065 filter cake Substances 0.000 claims abstract description 32
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 16
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910003450 rhodium oxide Inorganic materials 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- -1 triphenylphosphine fatty aldehyde Chemical class 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 9
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 6
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 claims description 6
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 3
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- QNGLQBPCJHRRCM-UHFFFAOYSA-N carbon monoxide;pentane-2,4-dione;rhodium;triphenylphosphane Chemical compound [Rh].[O+]#[C-].CC(=O)CC(C)=O.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QNGLQBPCJHRRCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 125000005595 acetylacetonate group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000000460 chlorine Substances 0.000 abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 230000000607 poisoning effect Effects 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002192 fatty aldehydes Chemical class 0.000 description 2
- 238000006170 formylation reaction Methods 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- QRSFFHRCBYCWBS-UHFFFAOYSA-N [O].[O] Chemical compound [O].[O] QRSFFHRCBYCWBS-UHFFFAOYSA-N 0.000 description 1
- ICFKJAPZLCYFIA-UHFFFAOYSA-N [Rh].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1 Chemical compound [Rh].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1 ICFKJAPZLCYFIA-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013522 chelant Substances 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, which comprises the steps of stirring and mixing rhodium oxide and acetylacetone, adding an initiator, heating to a reflux temperature for reaction, adding triphenylphosphine fatty aldehyde to continue to react at the reflux temperature after a system is changed from black to brown yellow, adding deionized water after the reaction is finished and cooling, filtering, washing a filter cake with the deionized water, and drying the filter cake in vacuum to obtain the acetylacetonatocarbonyltriphenylphosphine rhodium. The preparation method can prepare acetylacetonatocarbonyltriphenylphosphine rhodium with low content of chlorine impurities causing catalyst poisoning, and simultaneously, because acetylacetone is used as a reactant and a solvent in the reaction, the occurrence of side reaction is reduced, the obtained acetylacetonatocarbonyltriphenylphosphine rhodium product has high yield and high purity, does not need to be repeatedly washed, and can be directly applied after being dried.
Description
Technical Field
The invention relates to the field of noble metal catalyst synthesis, and particularly relates to a preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium.
Background
The rhodium catalyst is an important catalytic material and has been widely applied to the fields of petrochemical industry, pharmaceutical and chemical industry, fine chemical industry, environmental protection and the like in recent 30 years.
Acetylacetonatocarbonyltriphenylphosphine rhodium with the molecular formula Rh (C)5H7O2)(CO)(PPh3) ROPAC for short belongs to chelate rhodium organic matter coordinated by oxygen-oxygen ligand, has higher activity, higher selectivity and normal isomerization ratio for hydroformylation reaction of some olefins, has quite mild reaction condition and less side reaction, and is a main catalyst adopted by the current low-pressure oxo synthesis method.
The acetylacetonatocarbonyltriphenylphosphine rhodium is generally prepared from water and rhodium trichloride. According to the preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, disclosed in CN106674285B, a toluene solution of rhodium trichloride is used as a reaction system, carbon monoxide is used as a carbonyl source, and triphenylphosphine is added to synthesize a target product. The preparation method of the patent has the advantages of high rhodium single-pass conversion rate, simple and convenient process and mild conditions. However, the chlorine ions introduced by the reaction raw materials cannot be completely removed, so that the catalytic activity of the final product is influenced. According to the preparation method disclosed in J.chem.Soc.,1964,3156-3159, dichlorotetracarbonyldirhodium and acetylacetone are used as raw materials, petroleum ether is used as a solvent, sodium carbonate is added as an auxiliary agent, triphenylphosphine is added, and a product is obtained at a reflux temperature for a period of up to one week, wherein the yield based on metal rhodium in the raw material dichlorotetracarbonyldirhodium is 79%. The method can prepare acetylacetonatocarbonyltriphenylphosphine rhodium from dichlorotetracarbonyl rhodium, but the method has long reaction time and low product yield, and simultaneously, the product has low catalytic activity and short service life due to high chloride ion content.
In the method, a chlorine-containing rhodium compound is used as a starting material, a large amount of chloride ions are introduced into a reaction system, and partial raw materials are incompletely reacted and the chloride ions and rhodium are strongly charged and adsorbed, so that a large amount of chloride ions are easily introduced into a target product of acetylacetonatocarbonyltriphenylphosphine rhodium, and the acetylacetonatocarbonyltriphenylphosphine rhodium has low catalytic activity when used as an olefin formylation reaction, and is seriously poisoned by a catalyst. Therefore, a large amount of water is required to wash the chloride ions in the subsequent washing process to meet product standards. Although the yield of the acetylacetonatocarbonyltriphenylphosphino rhodium is improved to a certain extent by technical improvement and condition control, because the reaction period is long, the reaction condition is harsh, the rhodium black without catalytic activity and the chloride ion exceeding standard are easily introduced, the intermediate product is recrystallized by using an organic solvent, and the product treatment needs to be repeatedly washed by a large amount of water.
In addition, numerous patents at home and abroad clearly indicate that chlorine can cause acetylacetonatocarbonyltriphenylphosphine rhodium poisoning. Both at home and abroad, reports that the conversion rate of olefin is reduced and even the catalyst is poisoned to cause production halt due to over standard chloride ions in olefin formylation devices are provided. Rhodium is extremely sparsely distributed in the earth crust, difficult to exploit and enrich and high in cost, is the most expensive metal of platinum group metals, and has high recovery and refining cost due to the special chemical property of rhodium. Therefore, the method for preparing acetylacetonatocarbonyltriphenylphosphine rhodium with high yield and high purity has great significance.
Disclosure of Invention
The invention aims to provide a preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium with high yield and low chlorine content aiming at the technical problems of low yield and high chlorine content of the acetylacetonatocarbonyltriphenylphosphine rhodium.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
step one, mixing: in a three-neck flask with a reflux condenser, rhodium oxide and acetylacetone solution are stirred and mixed uniformly, a water ring vacuum pump is used, the three-neck flask is continuously evacuated under the vacuum degree of-0.08 Mpa and nitrogen with the pressure of 0.02Mpa is injected for three times, so that the oxygen content in the three-neck flask is less than 1000ppm, and by-products generated by overhigh oxygen content are prevented from reducing the purity of products; the rhodium content in the rhodium oxide is 82.5 percent; the mass ratio of the acetylacetone solution to the rhodium is 6-10;
step two, refluxing: adding an initiator into the mixed solution prepared in the first step, refluxing and stirring for 1.5h at the temperature of 120-140 ℃, adding an aliphatic aldehyde solution dissolved with triphenylphosphine to continue reacting at the reflux temperature of 120-140 ℃ after the solution changes from black to brown, stirring and reacting for 1.5h, stopping heating and cooling to room temperature; the initiator is ammonia water, and the adding amount of the ammonia water is 1 ml;
step three, filtering and washing: adding deionized water into the solution prepared in the second step to separate the acetylacetone triphenylphosphine carbonyl rhodium from the acetylacetone organic phase, then filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: vacuum drying the filter cake in the third step to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.4 to 1.7ppm, and the yield is 96.5 to 97.4 percent.
Preferably, in the second step, the fatty aldehyde is selected from one of acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and hexanal, and the mass ratio of the fatty aldehyde to rhodium is 0.5-2.
Preferably, the mass ratio of triphenylphosphine to rhodium in the second step is 2.8-3.8.
Preferably, the mass ratio of the deionized water to the acetylacetone in the step three is 0.5.
Preferably, the vacuum drying temperature in the fourth step is 30 ℃, and the vacuum degree is-0.06 MPa.
Compared with the prior art, the invention has the following advantages:
1. the acetylacetone and the aliphatic aldehyde are used as reactants and solvents, no other solvent is introduced into a reaction system, and the anhydrous reagent is used, so that the generation of byproducts is reduced, the product yield is improved, and the product purity is improved;
2. by adopting the rhodium raw material without chloride ions, the method ensures that no chlorine source is introduced in the whole reaction process, obtains acetylacetonatocarbonyltriphenylphosphine rhodium with low chlorine content, directly applies the rhodium to olefin carbonyl synthesis after drying, and omits the procedures of intermediate recrystallization, repeated washing of products and the like for removing chlorine.
Drawings
FIG. 1 is a process flow diagram of the preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium;
FIG. 2 is an infrared spectrum of triphenylphosphine carbonyl rhodium acetylacetonate prepared by the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with the rhodium content of 0.1g is dissolved in 0.6g of acetylacetone solution, after uniform stirring and mixing, a water ring vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 MPa and injecting nitrogen with the pressure of 0.02MPa for three times, thus realizing the oxygen content in the three-neck flask to be less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 120 ℃, stirring for 1.5h at the reflux temperature, injecting 0.28g of triphenylphosphine and 0.05 g of oxygen-free acetaldehyde after the solution is changed from black to brown yellow, continuously carrying out reflux reaction at 120 ℃, stopping heating after stirring and reacting for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.3g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.6ppm, and the yield is 97.3 percent.
Example 2
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: dissolving 0.122g of rhodium oxide with the rhodium content of 0.1g in 1g of acetylacetone solution in a three-neck flask provided with a reflux condenser, stirring and mixing uniformly, continuously evacuating under the vacuum degree of-0.08 MPa by using a water ring vacuum pump, and injecting nitrogen with the pressure of 0.02MPa for three times, so that the oxygen content in the three-neck flask is less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 120 ℃, stirring for 1.5h at the reflux temperature, injecting 0.31g of triphenylphosphine and 0.08 g of oxygen-free acetaldehyde once after the solution is changed from black to brown yellow, continuously carrying out reflux reaction at 120 ℃, stopping heating after stirring and reacting for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.7ppm, and the yield is 96.6 percent.
Example 3
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: dissolving 0.122g of rhodium oxide with the rhodium content of 0.1g in 1g of acetylacetone solution in a three-neck flask provided with a reflux condenser, stirring and mixing uniformly, continuously evacuating under the vacuum degree of-0.08 MPa by using a water ring vacuum pump, and injecting nitrogen with the pressure of 0.02MPa for three times, so that the oxygen content in the three-neck flask is less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 120 ℃, stirring for 1.5 hours at a reflux temperature, injecting 0.38g of triphenylphosphine and 0.2 g of oxygen-free propionaldehyde once after the solution is changed from black to brown-yellow, continuously carrying out reflux reaction at 120 ℃, stopping heating after stirring for reaction for 1.5 hours, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.6ppm, and the yield is 96.5 percent.
Example 4
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with the rhodium content of 0.1g is dissolved in 0.9g of acetylacetone solution, after uniform stirring and mixing, a water ring vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 MPa and injecting nitrogen with the pressure of 0.02MPa for three times, thus realizing the oxygen content in the three-neck flask to be less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 120 ℃, stirring for 1.5h at a reflux temperature, injecting 0.30g of triphenylphosphine and 0.12 g of oxygen-free butyraldehyde once after the solution is changed from black to brown yellow, continuing reflux reaction at 120 ℃, stopping heating after stirring reaction for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.45g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.4ppm, and the yield is 97.1 percent.
Example 5
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with the rhodium content of 0.1g is dissolved in 0.8g of acetylacetone solution, after uniform stirring and mixing, a water ring vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 MPa and injecting nitrogen with the pressure of 0.02MPa for three times, thus realizing the oxygen content in the three-neck flask to be less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 140 ℃, stirring for 1.5h at a reflux temperature, injecting 0.36g of triphenylphosphine and 0.2 g of oxygen-free valeraldehyde once after the solution is changed from black to brown yellow, continuously carrying out reflux reaction at 140 ℃, stopping heating after stirring and reacting for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.4g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.5ppm, and the yield is 96.7 percent.
Example 6
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with the rhodium content of 0.1g is dissolved in 1.0g of acetylacetone solution, after uniform stirring and mixing, a water ring vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 MPa and injecting nitrogen with the pressure of 0.02MPa for three times, thus realizing the oxygen content in the three-neck flask to be less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 130 ℃, stirring for 1.5h at the reflux temperature, injecting 0.3g of triphenylphosphine and 0.2 g of oxygen-free hexanal once after the solution is changed from black to brown yellow, continuously carrying out reflux reaction at 130 ℃, stopping heating after stirring for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.6ppm, and the yield is 97.4 percent.
Example 7
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with the rhodium content of 0.1g is dissolved in 1.0g of acetylacetone solution, after uniform stirring and mixing, a water ring vacuum pump is used for continuously evacuating under the vacuum degree of-0.08 MPa and injecting nitrogen with the pressure of 0.02MPa for three times, thus realizing the oxygen content in the three-neck flask to be less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 135 ℃, stirring for 1.5h at the reflux temperature, injecting 0.32g of triphenylphosphine and 0.18 g of oxygen-free acetaldehyde once after the solution is changed from black to brown yellow, continuously carrying out reflux reaction at 135 ℃, stopping heating after stirring and reacting for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.5ppm, and the yield is 97.2 percent.
Example 8
A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, 0.122g of rhodium oxide with the rhodium content of 0.1g is dissolved in 1.0g of acetylacetone solution, after uniform stirring and mixing, a water ring vacuum pump is used to continuously evacuate under the vacuum degree of-0.08 MPa and nitrogen with the pressure of 0.02MPa is injected for three times, thus realizing the oxygen content in the three-neck flask to be less than 1000 ppm;
step two, refluxing: adding 1ml of ammonia water into the mixed solution prepared in the first step, heating to 135 ℃, stirring for 1.5h at the reflux temperature, injecting 0.32g of triphenylphosphine and 0.16 g of oxygen-free acetaldehyde once after the solution is changed from black to brown yellow, continuously carrying out reflux reaction at 135 ℃, stopping heating after stirring and reacting for 1.5h, and cooling the solution to room temperature;
step three, filtering and washing: adding 0.5g of deionized water into the solution prepared in the second step, fully stirring until yellow solid is separated out from the mixed solution, filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: drying the filter cake obtained in the third step at 30 ℃ and under the vacuum degree of-0.06 MPa to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of the acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.5ppm, and the yield is 97.2 percent.
The product yields and the analytical results are shown in Table 1.
TABLE 1 product yield and analytical results Table
It can be concluded from the data in table 1 that examples 1 to 8 are the target of acetylacetonatocarbonyltriphenylphosphine rhodium with high yield and low chlorine impurity content, which can be obtained by the preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium provided by the present invention.
The determination spectrogram of the acetylacetonatocarbonyltriphenylphosphine rhodium product prepared by the invention is shown in figure 1 through an FT-IR instrument, is consistent with the publicly reported standard spectrogram of the acetylacetonatocarbonyltriphenylphosphine rhodium, and is determined to be the acetylacetonatocarbonyltriphenylphosphine rhodium.
Claims (5)
1. A preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium is characterized by comprising the following steps: the method comprises the following steps:
step one, mixing: in a three-neck flask with a reflux condenser, rhodium oxide and acetylacetone solution are stirred and mixed uniformly, a water ring vacuum pump is used, the three-neck flask is continuously evacuated under the vacuum degree of-0.08 Mpa and nitrogen with the pressure of 0.02Mpa is injected for three times, so that the oxygen content in the three-neck flask is less than 1000ppm, and by-products generated by overhigh oxygen content are prevented from reducing the purity of products; the rhodium content in the rhodium oxide is 82.5 percent; the mass ratio of the acetylacetone solution to the rhodium is 6-10;
step two, refluxing: adding an initiator into the mixed solution prepared in the first step, refluxing and stirring for 1.5h at the temperature of 120-140 ℃, adding an aliphatic aldehyde solution dissolved with triphenylphosphine to continuously react at the reflux temperature of 120-140 ℃ after the solution changes from black to brown, stirring and reacting for 1.5h, stopping heating and cooling to room temperature; the initiator is ammonia water, and the adding amount of the ammonia water is 1 ml;
step three, filtering and washing: adding deionized water into the solution prepared in the second step to separate the acetylacetone triphenylphosphine carbonyl rhodium from the acetylacetone organic phase, then filtering to obtain a filter cake, and washing the filter cake with deionized water again to remove impurities;
step four, drying: vacuum drying the filter cake in the third step to obtain acetylacetonatocarbonyltriphenylphosphine rhodium;
the purity of acetylacetonatocarbonyltriphenylphosphine rhodium is more than 99.9 percent, the content of chloride ions is 1.4 to 1.7ppm, and the yield is 96.5 to 97.4 percent.
2. The method for preparing acetylacetonatocarbonyltriphenylphosphine rhodium according to claim 1, wherein the aliphatic aldehyde in the second step is selected from acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde and hexanal, and the mass ratio of the aliphatic aldehyde to rhodium is 0.5-2.
3. The method for preparing acetylacetonatocarbonyltriphenylphosphine rhodium according to claim 1, wherein the mass ratio of triphenylphosphine to rhodium in the second step is 2.8-3.8.
4. The method for preparing acetylacetonatocarbonyltriphenylphosphine rhodium according to claim 1, wherein the mass ratio of deionized water to acetylacetonato in the third step is 0.5.
5. The method for preparing acetylacetonatocarbonyltriphenylphosphine rhodium according to claim 1, wherein the vacuum drying temperature in the fourth step is 30 ℃ and the vacuum degree is-0.06 MPa.
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| GB2075857A (en) * | 1980-05-15 | 1981-11-25 | Davy Mckee Oil & Chem | Making hydroformylation catalysts |
| CN101172987A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing 3-(triphenylphosphine )-carbonyl hydrogenation Rh |
| CN103709201A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonato dicarbonylrhodium, and olefin hydroformylation method |
| CN103709205A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, and olefin hydroformylation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2075857A (en) * | 1980-05-15 | 1981-11-25 | Davy Mckee Oil & Chem | Making hydroformylation catalysts |
| CN101172987A (en) * | 2006-10-31 | 2008-05-07 | 中国石油化工股份有限公司 | Method for producing 3-(triphenylphosphine )-carbonyl hydrogenation Rh |
| CN103709201A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonato dicarbonylrhodium, and olefin hydroformylation method |
| CN103709205A (en) * | 2012-10-09 | 2014-04-09 | 中国石油化工股份有限公司 | Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, and olefin hydroformylation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115651030A (en) * | 2022-10-28 | 2023-01-31 | 四川大学 | Method for synthesizing acetylacetonatocarbonyltriphenylphosphine rhodium by one-pot method |
| CN115651030B (en) * | 2022-10-28 | 2024-04-26 | 四川大学 | Method for synthesizing triphenylphosphine rhodium carbonyl acetylacetonate by one-pot method |
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