CN103709205A - Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, and olefin hydroformylation method - Google Patents
Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium, and olefin hydroformylation method Download PDFInfo
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Abstract
The invention discloses a preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium. The preparation method comprises following steps: (1) under precipitation reaction conditions, a rhodium trichloride aqueous solution is contacted with a precipitating agent so as to precipitate rhodium and obtain a sediment containing rhodium; (2) the sediment containing rhodium is washed until chloride ion content is less than 1000ppm; (3) under acetylacetonato dicarbonylrhodium synthesis conditions, the sediment containing rhodium, which is obtained in step (2), is dissolved, and is contacted with acetylacetone so as to obtain a reaction liquid containing acetylacetonato dicarbonylrhodium; and (4) under acetylacetonatocarbonyltriphenylphosphine rhodium synthesis conditions, acetylacetonatocarbonyltriphenylphosphine rhodium in the reaction liquid is contacted with triphenylphosphine. The invention also discloses an olefin hydroformylation method. The preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium is capable of reducing chloride ion content of products, increasing product synthesis yield, and improving catalytic activity of acetylacetonatocarbonyltriphenylphosphine rhodium.
Description
Technical field
The present invention relates to a kind of preparation method of acetylacetonatodicarrhodium rhodium and the method for olefin hydroformylation; being specifically related to a kind of employing Trichlororhodium hydrate is raw material; the precipitation that contains rhodium element by formation is prepared the method for acetylacetonatodicarrhodium rhodium again, and has comprised preparation method's the alkene of acetylacetonatodicarrhodium rhodium and the method that synthetic gas carries out hydroformylation reaction.
Background technology
Acetylacetonatodicarrhodium rhodium (Rh (acac) (PPh
3) (CO)) be alpha-olefin and synthetic gas (CO and H
2mixed gas) occur that hydroformylation reaction is just generating, the good catalyst precursor of isomery aldehyde.For example, propylene and synthetic gas are at Rh (acac) (PPh
3) (CO) under the existence of homogeneous catalyst precursor, generate butyraldehyde-n and isobutyric aldehyde; In addition can also be for Production of Acetic Acid by Methanol Carbonylation.
Prior art is at synthetic Rh (acac) (PPh
3) general minute two steps in process (CO): the first step is with Trichlororhodium hydrate (RhCl
3xH
2o) be starting raw material, react with methyl ethyl diketone, synthesis of acetyl acetone dicarbonyl rhodium (Rh (CO)
2(acac)).Second step is by Rh (CO)
2(acac) and triphenylphosphine reaction generate Rh (acac) (PPh
3) (CO).
< < prepares simple method > > (the Russian Chinese Journal of Inorganic Chemistry of rhodium dicarbonyl acetylacetonate (I), Wa Shaweisi is based on sand etc., 1967,12 (6), 1709) (Simple method of preparingacetylacetonate dicarbonylrhodium (I), Varshavskii Yu.S., ZhurnalNeorganicheskoi Khimii, 1967,12 (6), 1709) in, mentioned with RhCl
3xH
2o is raw material one-step synthesis Rh (CO)
2(acac).By RhCl
3xH
2o joins in dimethyl formamide (DMF) and dissolves as starting raw material, is heated to 150 ℃, treats RhCl
3xH
2o adds methyl ethyl diketone after all dissolving again, refluxes 1 hour, adds deionized waters more than several times, Rh (CO) after cooling
2(acac) flocks that takes on a red color is separated out.After filtering, with hexane recrystallization, obtain red and green color needle crystal, Rh (CO)
2(acac) yield is 75%.
Dicarbapentaborane-the beta-diketon of < < rhodium (I) and related compound > > (the Fu Bona base of a fruit and outstanding Wilkinson, Chemical Society's proceedings, 1964,3156-3160) (Dicarbonyl-β-diketonato-and RelatedComplexes of Rhodium (I), F.Bonati and G.Wilkinson, J.Chem.Soc.1964,3156-3160) in mentioned with RhCl
3xH
2o is the synthetic Rh (CO) of raw material two steps
2(acac).At 100 ℃, toward the RhCl of porphyrize
3xH
2in O, pass into carbon monoxide, obtain [Rh (CO)
2cl]
2, then with [Rh (CO)
2cl]
2for raw material, sherwood oil are solvent, add methyl ethyl diketone and barium carbonate to reflux at 100 ℃ 1 week.Through concentrating under reduced pressure, obtain red and green color needle-like Rh (CO)
2(acac) crystallization.Two steps are synthesized Rh (CO)
2(acac) total recovery is 85%.
In prior art, Rh (CO)
2(acac) and triphenylphosphine reaction generate Rh (acac) (PPh
3) (CO) be first by Rh (CO)
2(acac) and triphenylphosphine be dissolved in benzene solvent respectively, then the benzole soln of triphenylphosphine is joined to Rh (CO)
2(acac) in benzole soln, when reaction no longer includes after CO effusion, cooling solution is separated out yellow crystals, filters, uses benzene recrystallization, and productive rate is more than 96%.
CN102093432A discloses a kind of synthetic method of acetylacetonatodicarrhodium rhodium, described method is: (1) is by rhodium trichloride hydrate and N, dinethylformamide mixes, and under nitrogen protection, is heated to 130-150 ℃, after Trichlororhodium all dissolves, adding methyl ethyl diketone, be heated to back flow reaction 0.5-1.5h, reaction solution room temperature is being placed cooling, add precipitation toughener to separate out precipitation, precipitation aftertreatment makes rhodium dicarbonyl acetylacetonate; (2) the rhodium dicarbonyl acetylacetonate organic solvent dissolution of being prepared by step (1), adds triphenylphosphine, has Bubble formation, and after no longer including Bubble formation, reaction solution aftertreatment makes acetylacetonatodicarrhodium rhodium; Described organic solvent is straight-chain paraffin or the C6-C8 naphthenic hydrocarbon of C5-C10.In the method for this disclosure of the invention at synthetic Rh (CO)
2(acac) time, adding KCl or NaCl is precipitation agent, has improved Rh (CO)
2(acac) yield.
Although above-mentioned existing method can obtain higher Rh (acac) (PPh
3) (CO) yield, but use above-mentioned Rh (acac) (PPh
3) while (CO) carrying out propylene and synthetic gas generation hydroformylation reaction as catalyzer, find that the catalytic activity of catalyzer in the lower or reaction process of the catalytic activity of catalyzer declines clearly.Therefore, solve Rh (acac) (PPh
3) catalytic activity problem (CO) is that propylene and synthetic gas carry out the important problem that hydroformylation reaction faces.
Summary of the invention
The object of the invention is for propylene and synthetic gas, to carry out the low or catalytic activity of the hydroformylation reaction catalytic activity obvious problem that declines in order to overcome existing acetylacetonatodicarrhodium rhodium catalyzer; a kind of method of preparing the acetylacetonatodicarrhodium rhodium that catalytic activity is high is provided, a kind of method of the olefin hydroformylation that contains this acetylacetonatodicarrhodium rhodium preparation method is provided in addition.
The present inventor finds by research, existing rhodium dicarbonyl acetylacetonate and acetylacetonatodicarrhodium rhodium catalytic activity is low or catalytic activity reduces obviously, because the content of impurity chlorion in intermediate rhodium dicarbonyl acetylacetonate is higher, often be greater than 0.1 % by weight, and chlorion is the toxicant of catalyzer in hydroformylation reaction, even if from acetylacetonatodicarrhodium rhodium itself or other raw material to propylene and the synthetic gas chlorion (in cl content in reaction solution) that carries out bringing into hydroformylation reaction system 1ppm also can make rhodium catalyst poisoning rapidly.For this reason, need to reduce the chloride ion content in acetylacetonatodicarrhodium rhodium as far as possible.
Although prior art also can reduce the chloride ion content in acetylacetonatodicarrhodium rhodium by the mode of recrystallization intermediate rhodium dicarbonyl acetylacetonate, just reduced like this synthesis yield of acetylacetonatodicarrhodium rhodium product.And rhodium is the precious metal that a kind of price is extremely expensive, therefore higher yield is the key point that realizes acetylacetonatodicarrhodium rhodium batch production.
To this, the present inventor is by further research discovery, in acetylacetonatodicarrhodium rhodium preparation method's process, first Trichlororhodium is prepared into the precipitation containing rhodium element through precipitin reaction, chloride ions displace is got off, and by further filtering, washing reduces the content containing chlorion in the precipitation of rhodium element, carry out again the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, can guarantee like this in the process of follow-up synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, to less introducing chlorion in product, therefore not only can make the chloride ion content of acetylacetonatodicarrhodium rhodium product qualified, and owing to having reduced the repeatedly recrystallization carrying out for reducing chloride ion content in prior art, thereby also improved the synthesis yield that obtains acetylacetonatodicarrhodium rhodium product.Complete thus the present invention.
To achieve these goals, the invention provides a kind of preparation method of acetylacetonatodicarrhodium rhodium, it is characterized in that, the method comprises:
(1), under precipitin reaction condition, the Trichlororhodium aqueous solution is contacted with precipitation agent, so that rhodium element precipitation obtains the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3), under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, what step (2) was obtained describedly contacts with methyl ethyl diketone containing after the resolution of precipitate of rhodium element, obtains the reaction solution that contains rhodium dicarbonyl acetylacetonate;
(4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the rhodium dicarbonyl acetylacetonate in the described reaction solution that contains rhodium dicarbonyl acetylacetonate is contacted with triphenylphosphine.
The present invention also provides a kind of method of olefin hydroformylation; the method comprises prepares acetylacetonatodicarrhodium rhodium; and by the described acetylacetonatodicarrhodium rhodium making the hydroformylation reaction for alkene and synthetic gas; it is characterized in that the preparation method of the acetylacetonatodicarrhodium rhodium that the method for preparing acetylacetonatodicarrhodium rhodium provides for the invention described above.
By technique scheme provided by the invention, the content of the chlorion in the acetylacetonatodicarrhodium rhodium product preparing is less than 10ppm, and the synthesis yield of acetylacetonatodicarrhodium rhodium is greater than 95%.In embodiment 3, through Trichlororhodium being carried out after precipitin reaction is precipitated as rhodium hydroxide precipitation again to the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, chloride ion content in the acetylacetonatodicarrhodium rhodium product obtaining only has 6.5ppm, and in rhodium, synthesis yield reaches 98.2%.And the acetylacetonatodicarrhodium rhodium that uses prior art to prepare in comparative example 2 not only needs recrystallization, and in the product obtaining, chloride ion content has reached 95ppm, and in rhodium, yield also only has 87.4%.Therefore, technical scheme provided by the invention can solve detrimental impurity chloride ion content height and the low problem of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl yield effectively, realizes goal of the invention of the present invention.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The preparation method who the invention provides a kind of acetylacetonatodicarrhodium rhodium, is characterized in that, the method comprises:
(1), under precipitin reaction condition, the Trichlororhodium aqueous solution is contacted with precipitation agent, so that rhodium element precipitation obtains the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3), under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, what step (2) was obtained describedly contacts with methyl ethyl diketone containing after the resolution of precipitate of rhodium element, obtains the reaction solution that contains rhodium dicarbonyl acetylacetonate;
(4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the rhodium dicarbonyl acetylacetonate in the described reaction solution that contains rhodium dicarbonyl acetylacetonate is contacted with triphenylphosphine.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (1) is for being the precipitation containing containing rhodium element by Trichlororhodium hydrate deposition, can comprise first Trichlororhodium hydrate being dissolved into and in water, make the Trichlororhodium aqueous solution, then under precipitin reaction condition, in the Trichlororhodium aqueous solution, add precipitation agent to carry out precipitin reaction, obtain the precipitation containing rhodium element, control the temperature of precipitin reaction, the pH value of the reaction mixture of the precipitation containing rhodium element that control precipitin reaction obtains, to guarantee that the rhodium in the Trichlororhodium aqueous solution precipitates completely, obtain containing the reaction mixture containing the precipitation of rhodium element.
According to the present invention, the described precipitation agent of use can be any precipitation agent that can from Trichlororhodium hydrate, rhodium be precipitated out to contain the form of the precipitation of rhodium element.Under preferable case, described precipitation agent is ammoniacal liquor and/or alkali metal hydroxide, preferably one or more in NaOH, KOH and ammoniacal liquor.In these cases, described containing the yellow rhodium hydroxide precipitation of being precipitated as of rhodium element.
According to the present invention, the described precipitation agent of use can be used with solution form, and the concentration of precipitant solution can be selected in relative broad range, and under preferable case, described precipitation agent be take the solution form that volumetric molar concentration is 0.1-5mol/L and used; Preferred described precipitation agent be take the solution form that volumetric molar concentration is 1-3mol/L and is used.Wherein, when described precipitation agent is ammoniacal liquor, described precipitation agent is usingd solution form that volumetric molar concentration is 1-3mol/L and is used and refer to and use ammoniacal liquor that volumetric molar concentration is 1-3mol/L as precipitation agent.In the present invention, the concentration of ammoniacal liquor is continued to use the common implication in this area.
According to the present invention, Trichlororhodium hydrate dissolves while forming the described Trichlororhodium aqueous solution with water, and under preferable case, in the described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 0.1-5mol/L; In the preferred described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 1-3mol/L.
According to the present invention, the condition of described precipitin reaction is complete can be conducive to containing the precipitation of rhodium element, and can reduce the loss of rhodium, under preferable case, the condition of described precipitin reaction comprises: precipitation temperature is 5-10 ℃, the consumption of precipitation agent makes pH value after precipitin reaction between 7-10, and preferably pH value is between 7-8.
According to the present invention, under precipitin reaction condition, in the Trichlororhodium aqueous solution, add precipitation agent to carry out precipitin reaction, described in add and can carry out by any way, under preferable case, described in be incorporated as dropping.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (2) for further reducing the chlorion of the described precipitation containing rhodium element on the basis of precipitin reaction, can comprise first the reaction mixture containing containing the precipitation of rhodium element is carried out to solid-liquid separation, isolate the precipitation containing rhodium element, then the precipitation containing rhodium element that washing and filtering obtains, control wash temperature, control medium and number of times that washing is used, so that the content containing chlorion in the precipitation of rhodium element after washing is lower than 1000ppm, preferably lower than 500ppm.In the present invention, ppm refers to quality hundred content very much.
In the present invention, can detect the content containing chlorion in the precipitation of rhodium element by inductivity coupled plasma mass spectrometry (ICP-MS) mode.The precipitation containing rhodium element after washing is preferably carried out vacuum-drying in order to follow-up use at 25 ℃.
According to the present invention, described washing can be used conventional washing methods, controls wash conditions to realize better washing effect and to make rhodium loss few, under preferable case, makes successively to wash with water 2-5 time, hexanaphthene and washs 1 time, and wash temperature is 5-10 ℃.
According to the present invention, the described solid-liquid separation that the reaction mixture containing containing the precipitation of rhodium element is carried out can be any method, and under preferable case, described solid-liquid separation is filtration under diminished pressure.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (3) is for the building-up reactions of rhodium dicarbonyl acetylacetonate, can comprise first adds organic solvent to dissolve the precipitation containing rhodium element of having washed, obtain containing the mixture containing the precipitation of rhodium element, can keep containing the solution boiling containing the precipitation of rhodium element by the solution containing containing the precipitation of rhodium element is heated to more than 140 ℃, make all to dissolve containing the precipitation of rhodium element; Then under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, under reflux state, slowly add methyl ethyl diketone to carry out building-up reactions in the solution containing containing the precipitation of rhodium element.Add after methyl ethyl diketone, continue to keep the reaction of synthesis of acetyl acetone dicarbonyl rhodium at boiling, reflux state, control reaction times and temperature of reaction, obtain the reaction solution that contains rhodium dicarbonyl acetylacetonate.Stop building-up reactions, carry out aftertreatment, first the cooling reaction solution that contains rhodium dicarbonyl acetylacetonate, then the chilled reaction solution that contains rhodium dicarbonyl acetylacetonate is poured in deionized water, produce the precipitation of red cotton-shaped rhodium dicarbonyl acetylacetonate, then filter the precipitation of rhodium dicarbonyl acetylacetonate, remove the organic solvent dissolving containing the precipitation of rhodium element, then use other organic solvent washing, final drying obtains rhodium dicarbonyl acetylacetonate.
According to the present invention, after described precipitin reaction, by the described precipitation containing rhodium element obtaining, as starting raw material, carry out successively the reaction of synthesis of acetyl acetone dicarbonyl rhodium and synthesis of acetyl acetone triphenylphosphine rhodium carbonyl.The condition of described building-up reactions can be the condition known to those skilled in the art.
According to the present invention, the described precipitation containing rhodium element is joined in organic solvent and dissolved, obtain containing the solution containing the precipitation of rhodium element, under preferable case, the organic solvent that dissolves the described precipitation containing rhodium element is dimethylformamide, with respect to the rhodium element of 1 mole, the consumption of dimethylformamide is 1-3L; Preferably the consumption of dimethylformamide is 1.5-2L.Described dimethylformamide can be DMF and/or N,N-dimethylacetamide, is preferably DMF.
According to the present invention, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium, can obtain described rhodium dicarbonyl acetylacetonate, under preferable case, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium comprises: the mol ratio of described methyl ethyl diketone and rhodium is 8-15:1, temperature of reaction is 140-160 ℃, and the reaction times is 50-90 minute; The mol ratio of preferred described methyl ethyl diketone and rhodium is 9-12:1, and temperature of reaction is 150 ℃.
According to the present invention, after completing the reaction of described synthesis of acetyl acetone dicarbonyl rhodium, the reaction solution that contains rhodium dicarbonyl acetylacetonate described in reaction is obtained carries out aftertreatment.First be cooled to 5-10 ℃, then import the red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation of generation in 5-10 ℃ of water, described water is preferably deionized water.Then by filtration, remove described in above-mentioned dissolving the described organic solvent containing the precipitation of rhodium element, obtain the crude product of described rhodium dicarbonyl acetylacetonate.
According to the present invention, in order further to remove the impurity of rhodium dicarbonyl acetylacetonate precipitation surface, under preferable case, also the rhodium dicarbonyl acetylacetonate precipitation obtaining is washed, the solvent that described washing is used is not for dissolving the organic solvent of described rhodium dicarbonyl acetylacetonate precipitation, under preferable case, described organic solvent is normal hexane or hexanaphthene.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (4) is for by rhodium dicarbonyl acetylacetonate synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, can comprise first the rhodium dicarbonyl acetylacetonate obtaining is dissolved in organic solvent, obtain the solution that contains rhodium dicarbonyl acetylacetonate; Triphenylphosphine dissolved is obtained in organic solvent to the organic solution that contains triphenylphosphine simultaneously.Then the solution that heating contains rhodium dicarbonyl acetylacetonate, to the temperature of reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, then slowly adds by the organic solution that contains triphenylphosphine the reaction of carrying out synthesis of acetyl acetone triphenylphosphine rhodium carbonyl in the solution that contains rhodium dicarbonyl acetylacetonate.While carrying out the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, there is CO Bubble formation, control the condition of reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl until no longer produce CO bubble, obtain the reaction solution that contains acetylacetonatodicarrhodium rhodium.Stop the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, carry out aftertreatment, first by the cooling yellow crystals of separating out acetylacetonatodicarrhodium rhodium of the reaction solution that contains acetylacetonatodicarrhodium rhodium, then filter, wash and be dried, obtaining the finished product of acetylacetonatodicarrhodium rhodium.
According to the present invention, described in obtaining respectively, contain rhodium dicarbonyl acetylacetonate solution and described in contain triphenylphosphine organic solution in the organic solvent that uses can be the same or different, preferably use identical organic solvent, described organic solvent is one or more in normal hexane, hexanaphthene, benzene and toluene.The volumetric molar concentration of described rhodium dicarbonyl acetylacetonate in organic solvent is 0.2-0.5mol/L, and the volumetric molar concentration of described triphenylphosphine in organic solvent is 0.5-1.0mol/L.
According to the present invention, when the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out, under preferable case, the mol ratio of described rhodium dicarbonyl acetylacetonate and described triphenylphosphine is 1:1.1-2.0.
According to the present invention, while carrying out the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the solution that contains rhodium dicarbonyl acetylacetonate described in heating, then the organic solvent that contains triphenylphosphine described in slowly adding, and there is a CO Bubble formation, reaction is stirred and carried out until no longer include CO Bubble formation, stopped reaction.Under optimum condition, the temperature of reaction of carrying out the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is 70-80 ℃.
According to the present invention, in carrying out the reaction of described synthesis of acetyl acetone dicarbonyl rhodium and the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, can use rare gas element to prevent rhodium and the airborne oxygen generation oxidizing reaction in described rhodium dicarbonyl acetylacetonate and described acetylacetonatodicarrhodium rhodium, under preferable case, under each comfortable nitrogen atmosphere of reaction of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium and described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, carry out.
According to the present invention, after completing the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the reaction solution that contains acetylacetonatodicarrhodium rhodium described in reaction is obtained, be cooled to 5-10 ℃, separate out yellow crystals, then filter and obtain acetylacetonatodicarrhodium rhodium crystal, and at 5-10 ℃ with organic solvent washing, described organic solvent is not for dissolving the material of described acetylacetonatodicarrhodium rhodium, under preferable case, described organic solvent is one or more in normal hexane, hexanaphthene, benzene.Finally, by the vacuum-drying at 25 ℃ of described acetylacetonatodicarrhodium rhodium crystal, obtain described acetylacetonatodicarrhodium rhodium finished product.
According to the present invention, by the preparation method of described acetylacetonatodicarrhodium rhodium, the chloride ion content in the described acetylacetonatodicarrhodium rhodium obtaining is lower than 10ppm.
The present invention also provides a kind of olefin hydroformylation method; the method comprises prepares acetylacetonatodicarrhodium rhodium; and by the described acetylacetonatodicarrhodium rhodium making the hydroformylation reaction for alkene and synthetic gas; it is characterized in that the preparation method that the method for preparing acetylacetonatodicarrhodium rhodium is described acetylacetonatodicarrhodium rhodium.
According to the present invention, the preparation method that the method for preparing acetylacetonatodicarrhodium rhodium is described acetylacetonatodicarrhodium rhodium described above, does not repeat them here.
According to the present invention, the method for described hydroformylation of olefin and condition are content known in those skilled in the art, can be any method and corresponding conditions that can realize this reaction.In the present invention, described hydroformylation of olefin adopts rhythmic reaction method, and the method comprises: (1) by acetylacetonatodicarrhodium rhodium, part and organic solvent by a certain amount of autoclave of putting into; (2) under certain temperature, pressure condition, by raw material olefin, H
2continue by a certain percentage to pass in autoclave to react with CO.
By under certain catalyst solution concentration (in rhodium element), the mole number that in the unit time, in per volume of catalyst solution, reaction mass (in alkene) consumes calculates the rate of catalysis reaction of hydroformylation of olefin.The rate of catalysis reaction obtaining is the initial reaction rate of the hydroformylation of olefin under this catalyst solution concentration.
Described part, for can form with acetylacetonatodicarrhodium rhodium the P contained compound of rhodium-phosphine complex, can be single phosphine or biphosphine ligand, and part can have one or more identical or different substituted radicals, and under preferable case, described part is triphenylphosphine.
Described organic solvent be for can dissolve butyraldehyde-n and the isobutyric aldehyde that described propene hydroformylation reaction obtains, and can be one or more in benzene, toluene and trimerization butyraldehyde, is preferably trimerization butyraldehyde.
Described alkene can be the alkene of various routines, for example, can be the alkene of C2-C8.Most preferably, described alkene is propylene.
Described reaction conditions comprises that temperature is 100 ℃, and pressure is 0.55MPa.The ratio that described raw material passes into is propylene: H
2: CO=1:1:1(mol ratio).In the present invention, described pressure refers to absolute pressure.
According to the present invention, the method for described olefin hydroformylation is the hydroformylation reaction of alkene and synthetic gas, and under preferable case, described hydroformylation of olefin is that propylene generates reacting of butyraldehyde-n and isobutyric aldehyde with synthetic gas generation hydroformylation reaction.
In the present invention by precipitin reaction, rhodium in the Trichlororhodium aqueous solution is transformed into the precipitation containing rhodium element, make to prepare in the chemical constitution of building-up reactions raw material of rhodium dicarbonyl acetylacetonate and do not contain chlorine element, further washing step can be removed chlorion residual in precipitation, thereby reduces the content of chlorion in the finished product acetylacetonatodicarrhodium rhodium.In the present invention, owing to having reduced rhodium dicarbonyl acetylacetonate re-crystallization step, improved the synthesis yield of acetylacetonatodicarrhodium rhodium, and the chloride ion content in product significantly reduces.
Below will describe the present invention by embodiment, but the present invention is not limited to this.
In following examples, chlorion mass content is used the 7500CX icp ms (ICP-MS) of Agilent company to analyze.
The rhodium dicarbonyl acetylacetonate product preparing is measured by Fourier transformation infrared spectrometer, with standard spectrogram (Aldrich Alcohols and Phenols the composes storehouse) contrast of rhodium dicarbonyl acetylacetonate, determine that the product preparing is rhodium dicarbonyl acetylacetonate.Infrared spectroscopy adopts the THERMOFISHER SCIENTIFIC NICOLET NEXUS 470FT-IR of company instrument, adopts KBr pressed disc method to measure.
The finished product that prepare are measured by Fourier transformation infrared spectrometer, with standard spectrogram (Aldrich Alcohols and Phenols the composes storehouse) contrast of acetylacetonatodicarrhodium rhodium, determine that the product preparing is acetylacetonatodicarrhodium rhodium.Infrared spectroscopy adopts the THERMOFISHER SCIENTIFIC NICOLET NEXUS 470FT-IR of company instrument, adopts KBr pressed disc method to measure.
The content of rhodium in analysed preparation acetylacetonatodicarrhodium rhodium, the AAnalyst of Perkinelmer Inc. 400 type Atomic Absorption Spectroscopy AASs are analyzed.In the catalyzer using in hydroformylation of olefin, in the quality of rhodium element (g)=acetylacetonatodicarrhodium rhodium, content (quality the %) * acetylacetonatodicarrhodium rhodium of rhodium adds quality (g).
The content of rhodium in analysed preparation rhodium dicarbonyl acetylacetonate, the AAnalyst of Perkinelmer Inc. 400 type Atomic Absorption Spectroscopy AASs are analyzed.In the catalyzer using in hydroformylation of olefin, in the quality of rhodium element (g)=rhodium dicarbonyl acetylacetonate, content (quality the %) * rhodium dicarbonyl acetylacetonate of rhodium adds quality (g).
The synthesis yield of acetylacetonatodicarrhodium rhodium product, in rhodium element, calculates according to the following formula:
The synthesis yield of rhodium dicarbonyl acetylacetonate product, in rhodium element, calculates according to the following formula:
The raw material using in following examples and comparative example is commercially available acquisition all.
Embodiment 1
The present embodiment is for illustrating the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
(1) precipitin reaction: in 1500ml beaker, add the Trichlororhodium aqueous solution that 250.00ml Rh concentration is 1.000mol/L, under magnetic agitation, controlling temperature of reaction is 10 ℃, the about 750ml of NaOH solution that dropping concentration is 1.00mol/L, monitoring pH changes, and stops dripping when pH=8.0, obtains the reaction soln that contains rhodium hydroxide precipitation.
(2) washing precipitation: will contain the reaction soln filtration under diminished pressure of rhodium hydroxide precipitation, isolate rhodium hydroxide precipitation.By temperature, be the deionized water wash three times of 10 ℃, finally with 10 ℃ of hexanaphthenes washings one time.25 ℃ of vacuum-dryings, obtain yellow rhodium hydroxide precipitation.The content of measuring chlorion in rhodium hydroxide precipitation is 495ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first the rhodium hydroxide precipitation of gained is put into three mouthfuls of reaction flasks that 1000ml is provided with reflux exchanger.Add 375ml analytical pure DMF; Stir; Be heated to 150 ℃, boiling; Under total reflux state, treat the dissolving completely of rhodium hydroxide precipitation, obtain containing the solution that rhodium hydroxide precipitates, solvent is DMF, in solution, the volumetric molar concentration of rhodium is 0.666mol/L.
Then carry out the reaction of synthesis of acetyl acetone dicarbonyl rhodium.In the solution that contains rhodium hydroxide precipitation, slowly add 225 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 9:1.Control reaction heating 150 ℃, reflux, and pass into nitrogen protection reaction and stop after 50 minutes.Obtain the reaction solution that contains rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 10 ℃, be poured into and fill in the beaker that 3100ml temperature is 10 ℃ of deionized waters, generate red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Remove by filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product preparing, with the washing of 10 ℃ of normal hexanes, then vacuum-drying at 25 ℃, obtain being 62.0 grams of the crystal finished products of red and green color.Fourier infrared spectrograph is measured to the spectrogram that crystal finished product obtains, with the standard spectrogram contrast of rhodium dicarbonyl acetylacetonate, determine that crystal finished product is rhodium dicarbonyl acetylacetonate.
(4) synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: first rhodium dicarbonyl acetylacetonate crystal 62.0g is added to the heating of 1.2L hexanaphthene, stir, be warming up to 70 ℃, it is dissolved completely, obtain the solution that contains rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.20mol/L.Simultaneously by 70g triphenylphosphine dissolved in 530ml hexanaphthene, obtain the organic solvent that contains triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 0.50mol/L.
Then carry out the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl.Under agitation; isothermal reaction at 70 ℃; in the solution that contains rhodium dicarbonyl acetylacetonate obtained above, drip the cyclohexane solution 530ml that above-mentioned triphenylphosphine concentration is 0.50mol/L; wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:1.11; carry out building-up reactions; and passing into nitrogen protection, reaction has CO Bubble formation.Question response does not have after CO Bubble formation, and stopped reaction obtains the reaction solution that contains acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 10 ℃, separates out yellow crystals.Filtration obtains yellow crystals, with the cyclohexane solution washings of 10 ℃ 3 times, then 25 ℃ of vacuum-dryings, obtains 117.8 grams of the finished product.Fourier infrared spectrograph is measured to the spectrogram that the finished product obtain, with the standard spectrogram contrast of acetylacetonatodicarrhodium rhodium, determine that the finished product are acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 2
The present embodiment is for illustrating the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
(1) precipitin reaction: in 1000ml beaker, add the Trichlororhodium aqueous solution that 150.0ml Rh concentration is 2.000mol/L.Under magnetic agitation, controlling temperature of reaction is 7 ℃, the about 300ml of KOH solution that dropping concentration is 3.00mol/L, and monitoring pH changes, and stops dripping when pH=7.0, obtains the reaction soln that contains rhodium hydroxide precipitation.
(2) washing precipitation: will contain the reaction soln filtration under diminished pressure of rhodium hydroxide precipitation, isolate rhodium hydroxide precipitation.By temperature, be the deionized water wash three times of 8 ℃, finally with 7 ℃ of hexanaphthenes washing washings one time.25 ℃ of vacuum-dryings, the yellow rhodium hydroxide precipitation obtaining.The content of measuring chlorion in rhodium hydroxide precipitation is 450ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first gained rhodium hydroxide precipitation is put into three mouthfuls of reaction flasks that 1500ml is provided with reflux exchanger.Add 600ml analytical pure DMF, stir, be heated to 150 ℃, boiling; Under total reflux state, treat the dissolving completely of rhodium hydroxide precipitation, obtain containing the solution that rhodium hydroxide precipitates, solvent is DMF, in solution, the volumetric molar concentration of rhodium is 0.50mol/L.
Then carry out the reaction of synthesis of acetyl acetone dicarbonyl rhodium.In the solution that contains rhodium hydroxide precipitation, slowly add 360 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 12:1.Control reaction heating 150 ℃, reflux, reaction stops after 90 minutes, obtains the reaction solution that contains rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 7 ℃, be poured into and fill in the beaker that 5800ml temperature is 7 ℃ of deionized waters, generate red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Remove by filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product preparing, with vacuum-drying at the washing of 7 ℃ of normal hexanes, 25 ℃, obtain being 76.0 grams of the crystal finished products of red and green color.Determine that crystal finished product is rhodium dicarbonyl acetylacetonate.
(4) synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: first rhodium dicarbonyl acetylacetonate crystal 76.0g is added to the heating of 0.59L normal hexane, stir, be warming up to 75 ℃, it is dissolved completely, obtain the solution that contains rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.50mol/L.Simultaneously by 154g triphenylphosphine dissolved in 587ml normal hexane, obtain the organic solvent that contains triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 1.00mol/L.
Then carry out the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl.Under agitation, isothermal reaction at 80 ℃, in the solution that contains rhodium dicarbonyl acetylacetonate obtained above, drip the cyclohexane solution 587ml that above-mentioned triphenylphosphine concentration is 1.00mol/L, wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:2.0, carry out building-up reactions, and have CO Bubble formation.Question response does not have after CO Bubble formation, and stopped reaction obtains the reaction solution that contains acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 7 ℃, separates out yellow crystals.Filtration obtains yellow crystals, with the hexane solution washings of 7 ℃ 3 times, then 25 ℃ of vacuum-dryings, obtains 144.5 grams of the finished product.Determine that the finished product are acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 3
The present embodiment is for illustrating the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
(1) precipitin reaction: in tri-mouthfuls of reaction flasks of 1000ml, add the Trichlororhodium aqueous solution that 80ml Rh concentration is 2.500mol/L.Under magnetic agitation, controlling temperature of reaction is 5 ℃, the about 300ml of ammonia soln that dropping concentration is 2.00mol/L, and monitoring pH changes, and stops dripping when pH=7.5, obtains the reaction soln that contains rhodium hydroxide precipitation.
(2) washing precipitation: will contain the reaction soln filtration under diminished pressure of rhodium hydroxide precipitation, isolate rhodium hydroxide precipitation.By temperature, be the deionized water wash three times of 5 ℃, finally with 5 ℃ of hexanaphthenes washings one time.25 ℃ of vacuum-dryings, the yellow rhodium hydroxide precipitation obtaining.The content of measuring chlorion in rhodium hydroxide precipitation is 410ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first gained rhodium hydroxide precipitation is put into three mouthfuls of reaction flasks that 1000ml is provided with reflux exchanger, add 360ml analytical pure DMF, stir, be heated to 150 ℃, boiling, under total reflux state, treats the dissolving completely of rhodium hydroxide precipitation, obtain the solution that contains rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.55mol/L.
Then carry out the reaction of synthesis of acetyl acetone dicarbonyl rhodium.In the solution that contains rhodium hydroxide precipitation, slowly add 210 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 10.5:1.Control reaction heating 150 ℃, reflux, reaction stops after 80 minutes, obtains the reaction solution that contains rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 5 ℃, be poured into and fill in the beaker that 5800ml temperature is 5 ℃ of deionized waters, generate red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Remove by filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product preparing, with the washing of 5 ℃ of hexanaphthenes, then vacuum-drying at 25 ℃, obtain being 51.2 grams of the crystal finished products of red and green color.Determine that crystal finished product is rhodium dicarbonyl acetylacetonate.
(4) synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: first rhodium dicarbonyl acetylacetonate crystal 51.2g is added to the heating of 0.566L benzene, stir, be warming up to 80 ℃, it is dissolved completely, obtain the solution that contains rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.35mol/L.Simultaneously by 83g triphenylphosphine dissolved in 422ml benzene, obtain the organic solvent that contains triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 0.75mol/L.
Then carry out the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl.Under agitation, isothermal reaction at 75 ℃, in the solution that contains rhodium dicarbonyl acetylacetonate obtained above, drip the benzole soln 422ml that above-mentioned triphenylphosphine concentration is 0.75mol/L, wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:1.6, carry out building-up reactions, and have CO Bubble formation.Question response does not have after CO Bubble formation, and stopped reaction obtains the reaction solution that contains acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 5 ℃, separates out yellow crystals.Filtration obtains yellow crystals, with the benzole soln washings of 5 ℃ 3 times, then 25 ℃ of vacuum-dryings, obtains 97.7 grams of the finished product.Determine that the finished product are acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 4
The present embodiment is for illustrating the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
According to the method for embodiment 3, different, in precipitin reaction, monitoring pH changes, and stops dripping when pH=10, obtains the reaction soln that contains rhodium hydroxide.Product analysis the results are shown in Table 1.
Comparative example 1
According to the method for embodiment 3, different, there is no precipitin reaction step, washing precipitation step and synthesis of acetyl acetone triphenylphosphine rhodium carbonyl step.
In synthesis of acetyl acetone dicarbonyl rhodium step, the Trichlororhodium aqueous solution instead of hydrogen rhodium oxide precipitation that the 80ml Rh concentration of take is 2.500mol/L; After obtaining rhodium dicarbonyl acetylacetonate crude product, with normal hexane, carry out recrystallization secondary simultaneously.The chloride ion content of measuring synthetic rhodium dicarbonyl acetylacetonate, analytical results is in Table 1.
Comparative example 2
According to the method for embodiment 3, different, there is no precipitin reaction step and washing precipitation step.
In synthesis of acetyl acetone dicarbonyl rhodium step, the Trichlororhodium aqueous solution instead of hydrogen rhodium oxide precipitation that the 80ml Rh concentration of take is 2.500mol/L; After obtaining rhodium dicarbonyl acetylacetonate crude product, with normal hexane, carry out recrystallization secondary simultaneously.Measure the chloride ion content of synthetic acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 5
The present embodiment is for illustrating the method for olefin hydroformylation.
Get the acetylacetonatodicarrhodium rhodium 0.0477g that embodiment 1 prepares; 6.00 grams of triphenylphosphines and 44.00 grams of trimerization butyraldehyde are put into 100ml autoclave and are formed 50ml catalyst solution, to passing into propylene, hydrogen and CO in autoclave, carry out propene hydroformylation reaction.Carrying out propene hydroformylation reaction condition is: 100 ℃ of temperature, pressure 0.55MPa, propylene: H
2: CO=1:1:1(mol ratio), measure the initial rate of catalysis reaction of propene hydroformylation reaction.The results are shown in Table 2.
Embodiment 6
The present embodiment is for illustrating the method for olefin hydroformylation.
Get the acetylacetonatodicarrhodium rhodium 0.0477g that embodiment 2 prepares, according to the condition of embodiment 5, measure the initial rate of catalysis reaction of propene hydroformylation reaction.The results are shown in Table 2.
Embodiment 7
The present embodiment is for illustrating the method for olefin hydroformylation.
Get the acetylacetonatodicarrhodium rhodium 0.0477g that embodiment 3 prepares, according to the condition of embodiment 5, measure the initial rate of catalysis reaction of propene hydroformylation reaction.The results are shown in Table 2.
Comparative example 3
Get the rhodium dicarbonyl acetylacetonate 0.0254g that comparative example 1 prepares, according to the condition of embodiment 5, measure the initial rate of catalysis reaction of propene hydroformylation reaction.The results are shown in Table 2.
Comparative example 4
Get the acetylacetonatodicarrhodium rhodium 0.0477g that comparative example 2 prepares, according to the condition of embodiment 5, measure the initial rate of catalysis reaction of propene hydroformylation reaction.The results are shown in Table 2.
Table 1
| Numbering | Rhodium content (quality %) | Yield (%) | Chloride ion content (ppm, quality) |
| Embodiment 1 | 20.8 | 95.2 | 8.8 |
| Embodiment 2 | 20.8 | 97.3 | 7.8 |
| Embodiment 3 | 20.7 | 98.2 | 6.5 |
| Embodiment 4 | 20.7 | 92.1 | 9.9 |
| Comparative example 1 | 39.0 | 88.4 | 3200 |
| Comparative example 2 | 20.8 | 87.4 | 95 |
Table 2
Data by above-mentioned experimental result table 1 and table 2 can be found out, adopt the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention, and the acetylacetonatodicarrhodium rhodium product obtaining, has synthesis yield high, the feature that chloride ion content is low.As can be seen here, in technical scheme provided by the invention, the raw material of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is changed into rhodium precipitation, really can realize the present invention and reduce product chloride ion content, improve the goal of the invention of product synthesis yield.
Further by the acetylacetonatodicarrhodium rhodium product that adopts preparation method provided by the invention to obtain; apply to propene hydroformylation reaction; under the condition identical in quality of the rhodium using; because chlorine ion concentration is lower in reactor; can obtain initial rate of catalysis reaction faster, illustrate that the acetylacetonatodicarrhodium rhodium that preparation method of the present invention obtains can have better catalytic activity.
Embodiment 4 is the different of pH value in control precipitin reaction from the difference of embodiment 1.By experimental result, can be found out, the pH value that makes precipitin reaction for 7-8 be the preferred implementation that obtains preparation method's best effect of the present invention.
Claims (12)
1. a preparation method for acetylacetonatodicarrhodium rhodium, is characterized in that, the method comprises:
(1), under the condition of precipitin reaction, the Trichlororhodium aqueous solution is contacted with precipitation agent, so that rhodium element precipitation obtains the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3), under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, what step (2) was obtained describedly contacts with methyl ethyl diketone containing after the resolution of precipitate of rhodium element, obtains the reaction solution that contains rhodium dicarbonyl acetylacetonate;
(4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the rhodium dicarbonyl acetylacetonate in the described reaction solution that contains rhodium dicarbonyl acetylacetonate is contacted with triphenylphosphine.
2. method according to claim 1, wherein, described precipitation agent is ammoniacal liquor and/or alkali metal hydroxide.
3. method according to claim 1 and 2, wherein, in the described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium element is 0.1-5mol/L, described precipitation agent be take the solution form that volumetric molar concentration is 0.1-5mol/L and is used.
4. method according to claim 1, wherein, the condition of described precipitin reaction comprises: precipitation temperature is 5-10 ℃; The consumption of precipitation agent makes pH value after precipitin reaction between 7-10.
5. method according to claim 1, wherein, washing to described containing the chloride ion content in the precipitation of rhodium element, be lower than 500ppm.
6. method according to claim 5, wherein, described washing washing composition used is water or hexanaphthene, wash temperature is 5-10 ℃.
7. method according to claim 1, wherein, is dimethylformamide for dissolving the solvent of the described precipitation containing rhodium element, and with respect to the rhodium element of 1 mole, the consumption of dimethylformamide is 1-3L.
8. method according to claim 1, wherein, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium comprises: the mol ratio of described methyl ethyl diketone and rhodium element is 8-15:1; Temperature of reaction is 140-160 ℃, and the reaction times is 50-90 minute.
9. method according to claim 1, wherein, the condition of the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl comprises: the mol ratio of described rhodium dicarbonyl acetylacetonate and described triphenylphosphine is 1:1.1-2, temperature of reaction is 70-80 ℃.
10. according to the method described in any one in claim 1-9, wherein, under each comfortable nitrogen atmosphere of reaction of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium and synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, carry out.
The method of 11. 1 kinds of olefin hydroformylations; the method comprises prepares acetylacetonatodicarrhodium rhodium; and by the described acetylacetonatodicarrhodium rhodium making the hydroformylation reaction for alkene and synthetic gas; it is characterized in that, the method for preparing acetylacetonatodicarrhodium rhodium is the method described in any one in claim 1-10.
12. methods according to claim 11, wherein, described hydroformylation of olefin is that propylene generates reacting of butyraldehyde-n and isobutyric aldehyde with synthetic gas generation hydroformylation reaction.
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| CN105289736A (en) * | 2015-11-11 | 2016-02-03 | 天津渤化永利化工股份有限公司 | Preparation method of acetylacetone dioxaphosphepin |
| CN106749419A (en) * | 2016-11-18 | 2017-05-31 | 江西省汉氏贵金属有限公司 | Acetylacetone,2,4-pentanedione triphenyl phosphorus carbonyl closes the synthesis technique of rhodium |
| CN111333683A (en) * | 2020-04-09 | 2020-06-26 | 中国海洋石油集团有限公司 | Preparation method of acetylacetonatodicarbonylrhodium and mixed carbon-four hydroformylation method |
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| CN114591373A (en) * | 2022-03-17 | 2022-06-07 | 金川集团股份有限公司 | Preparation method of acetylacetonatocarbonyltriphenylphosphine rhodium |
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| 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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