Preparation process for molybdenum acetylacetonateTechnical field
The present invention relates to chemical field, specifically a kind of preparation process for molybdenum acetylacetonate.
Background technology
Acetylacetone acid molybdenum is the organic compound of an important molybdenum, is mainly used in the oxygen molybdenum compound of preparation Schiff's base.Reset synthetic pentenals with acetylacetone acid molybdenum catalysis methylbutynol, also have its catalysis dihydrodehydrolinalool to reset the preparation dihydrocitral.Use acetylacetone acid molybdenum to make oxide catalyst, luxuriant and rich with fragrance liquid-phase oxidation can be become phenanthrenequione.Acetylacetone acid molybdenum vinylbenzene load can be used as the catalyzer of tetrahydrobenzene with the synthetic epoxy cyclohexane of the quantitative epoxidation of tertbutyl peroxide, and it is the main raw material of synthetic three (pentafluorophenyl group) boron molybdenum oxide still.Acetylacetone acid molybdenum is by using as catalyzer more and more widely, but in China manufacturer do not arranged as yet, and the shortage of resources of molybdenum at present, price continuous rise on its world market.Rationally efficient the utilization, resource recovery is the target of exploitation acetylacetone acid molybdenum.
" fine chemistry industry " 2002 19 volume the 5th phases (the 291st～294 page), people such as the domestic Zhang Yadong of Zhengzhou University disclose with molybdic oxide and an amount of methyl ethyl diketone and have refluxed together, filtered while hot is removed unreacted molybdic oxide, and the filtrate impouring is separated out orange-yellow powder after freezing in organic solvent.Because methyl ethyl diketone is easily oxidized and self easy polymerization under reflux state in air, exists the product that unreacted molybdic oxide and side reaction generate in the product, product is impure, its rubicundity, and product yield is low, is 57.5～66.2%; Prepared acetylacetone acid molybdenum is used as catalyzer, do not reach expected effect.
Disclose with molybdic oxide in " American Chemical Society can will " nineteen fifty-nines 81 the 3188th page of the volume and be dissolved in the excessive ammonia, added methyl ethyl diketone, used 10%HNO3Transfer about PH to 3.5.Standing over night is separated out yellow crystal.Used organic bases ammoniacal liquor in this method, ammoniacal liquor is volatile, and is wayward, and pungency is strong, big for environment pollution, and difficulty is used widely in industry; Ammoniacal liquor and HNO3The ammonium nitrate explosive that generates, the danger during production is big; HNO3Be acid with strong oxidizing property, the product section oxidation can be influenced yield.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, the preparation process for molybdenum acetylacetonate that provides a kind of methyl ethyl diketone under low-temperature condition, to react, avoid the oxidized and generation self-polymerization of methyl ethyl diketone, improve product yield and purity.
For this reason, the present invention adopts following technical scheme: with weakly alkaline inorganic alkali solution molybdic oxide is dissolved, add antioxidant, be warmed up to 40～70 ℃, then drip methyl ethyl diketone, drip to finish the back with non-oxidizing mineral acid regulator solution to slightly acidic, be incubated then to separating out the acetylacetone acid molybdenum crystal; Cool off afterwards, filter, the methyl ethyl diketone that adheres on the filter cake is removed in rinsing.
As further technical scheme of the present invention, described antioxidant is butylated hydroxy anisole, butylated hydroxytoluene, Tenox PG or tertiarybutylhydroquinone.
As further technical scheme of the present invention, described mineral acid is that mass percent is dilute hydrochloric acid, dilute sulphuric acid or the phosphoric acid below 10%, and the pH value of weakly acidic solution is 3-5.
As further technical scheme of the present invention, described inorganic alkali solution is the sodium of yellow soda ash, salt of wormwood, sodium bicarbonate or dilute concentration or the oxyhydroxide of potassium, and its pH value is 9-11.
The present invention uses inorganic alkali solution, reaction safety, and environmental pollution is little, can be used widely in industry; Methyl ethyl diketone reacts with molybdic oxide under low-temperature condition, has avoided the self-polymerization of methyl ethyl diketone, and side reaction is few, product yield and purity height; Antioxidant avoids methyl ethyl diketone oxidized, and by product is few; With the pH value of non-oxidizing mineral acid regulator solution, avoided that nitric acid has further improved the yield of product to the oxidation of product in the existing method.
The invention will be further described below in conjunction with embodiment, but protection scope of the present invention is not limited to following embodiment.
Embodiment
Embodiment 1
Molybdic oxide 28.8g (0.2mol), yellow soda ash 31.8g (0.3mol), 200ml water, stirring and dissolving adds antioxidant BHA (butylated hydroxy anisole) 1.5g, warming-in-water to 60 ℃, drip methyl ethyl diketone 40g (0.4mol) again, the dropping time is controlled at 2h, drips to finish with 8% sulfuric acid (about 200ml) to regulate PH to 3～4, separate out light yellow crystal, then 50 ℃ of insulated and stirred 1.5h.Be cooled to 0 ℃, static 1 hour, suction filtration, washing filter cake were neutral to PH, use 50ml washing with alcohol filter cake at last, and 50 ℃ of vacuum decompression oven dry get the light yellow crystal acetylacetone acid molybdenum, 60g, yield 92%.
Embodiment 2
Molybdic oxide 28.8g (0.2mol), sodium hydroxide 10g (0.25mol), 80ml water, stirring and dissolving adds antioxidant TBHQ (tertiarybutylhydroquinone) 0.86g, warming-in-water to 40 ℃, drip methyl ethyl diketone 40g (0.4mol) again, the dropping time is controlled at 2h, drips to finish with 6% hydrochloric acid (about 200ml) to regulate PH to 3, separate out light oyster white crystal acetylacetone acid molybdenum, then 40 ℃ of insulated and stirred 2h.Be cooled to-5 ℃, suction filtration, washing filter cake are neutral to PH, use 50ml washing with alcohol filter cake at last, 50 ℃ of vacuum decompression oven dry, 61g, yield 93.5%.
Embodiment 3
Molybdic oxide 50g (0.347mol), salt of wormwood 48g (0.347mol), 250ml water, stirring and dissolving adds anti-oxidant BHT (butylated hydroxytoluene) 1.0g, warming-in-water to 70 ℃, drip methyl ethyl diketone 69.4g (0.694mol) again, the dropping time is controlled at 1h, drips to finish with 10% hydrochloric acid (about 250ml) to regulate PH to 3, separate out the yellow crystals acetylacetone acid molybdenum, then 70 ℃ of insulated and stirred 2h.Be cooled to-5 ℃, suction filtration, washing filter cake are neutral to PH, use 50ml washing with alcohol filter cake at last, 50 ℃ of vacuum decompression oven dry, 102g, yield 90%.