EP3802477A1 - Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre - Google Patents

Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre

Info

Publication number
EP3802477A1
EP3802477A1 EP19735369.1A EP19735369A EP3802477A1 EP 3802477 A1 EP3802477 A1 EP 3802477A1 EP 19735369 A EP19735369 A EP 19735369A EP 3802477 A1 EP3802477 A1 EP 3802477A1
Authority
EP
European Patent Office
Prior art keywords
hydroxide
oxide
acetylacetone
reaction
acetylacetonate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19735369.1A
Other languages
German (de)
English (en)
French (fr)
Inventor
Philippe Laubry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Compagnie Generale des Etablissements Michelin SCA
Original Assignee
Compagnie Generale des Etablissements Michelin SCA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Compagnie Generale des Etablissements Michelin SCA filed Critical Compagnie Generale des Etablissements Michelin SCA
Publication of EP3802477A1 publication Critical patent/EP3802477A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/77—Preparation of chelates of aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/92—Ketonic chelates
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table

Definitions

  • the invention relates to a process for the preparation of acetylacetonate of a hydrated or anhydrous chemical element from oxide or hydroxide of the chemical element, acetylacetone and water.
  • the invention also relates to a batch continuous process for the synthesis of such an acetylacetonate of a hydrated or anhydrous chemical element.
  • a known synthesis route of cobalt (II) acetylacetonate dihydrate (AA 2 Co, 2H 2 O) is to react acetylacetone in alkaline (Na, K) or pseudo-alkaline (ammonium) type enolate form with dichloride. of cobalt.
  • the disadvantage of this reaction is that it releases undesirable compounds, for example sodium chloride.
  • This document also describes the preparation of magnesium acetylacetonate dihydrate (AA 2 Mg, 2H 2 O) from magnesium chloride in an aqueous medium.
  • the magnesium hydroxide is formed by reaction between magnesium dichloride and potassium hydroxide.
  • the magnesium hydroxide reacts in mass (without solvent) with the acetylacetone in enol form in slight excess to lead to the magnesium acetylacetonate dihydrate (AA 2 Mg, 2H 2 0).
  • CN 1746180 also discloses a process for the preparation of cobalt (II) acetylacetonate dihydrate (AA 2 Co, 2H 2 O).
  • US6376719 and US6093844 disclose methods for obtaining anhydrous alkaline earth metal acetylacetonate mass and high temperature drying or under high vacuum. They do not make it possible to obtain a hydrated product.
  • the subject of the invention is therefore a process for preparing the acetylacetonate of a hydrated or anhydrous Me chemical element, wherein the chemical element Me is chosen from alkaline earth metals, transition metals and lanthanides, comprising a reaction step in an aqueous medium of the oxide or hydroxide of Me introduced in solid form and acetylacetone, acetylacetone being in excess relative to the oxide or the Me hydroxide.
  • hydrated acetylacetonate Me is meant a product which comprises one or more molecules of water generally designated by water of crystallization.
  • anhydrous Me acetylacetonate is meant a product which does not comprise water molecules.
  • oxide or hydroxide of Me we mean the chemical element
  • oxide or hydroxide of Me introduced in solid form means that the oxide or hydroxide of Me is not introduced into solution.
  • alkaline earth metals that can be used according to the invention, mention may be made of magnesium, calcium, strontium and barium.
  • transition metals that may be used according to the invention, mention may be made of cobalt, nickel, copper and zinc.
  • lanthanides that can be used according to the invention, mention may be made of lanthanum, cerium, praseodymium and neodymium.
  • the chemical element Me is preferably chosen from cobalt, magnesium, nickel, calcium, neodymium and zinc.
  • the chemical element Me is cobalt.
  • the compound obtained according to the process according to the invention is then acetylacetonate cobalt dihydrate (AA 2 Co, 2H20).
  • the precipitate of this compound has a pink salmon color.
  • this compound is obtained by reaction between cobalt (II) hydroxide (Co (OH) 2 ) and acetylacetone in water.
  • the chemical element Me is magnesium.
  • the compound obtained according to the process according to the invention is then magnesium acetylacetonate dihydrate (AA 2 Mg, 2H 2 O).
  • the precipitate of this compound has a white color.
  • this compound is obtained by reaction between magnesium (II) hydroxide (Mg (OH) 2 ) or magnesium oxide MgO and acetylacetone in water.
  • magnesium oxide When magnesium oxide is used as a starting material, it reacts with water to form magnesium (II) hydroxide (Mg (OH) 2 ) which in turn will react with acetylacetone in water for form the final product (AA 2 Mg, 2H 2 O).
  • the acetylacetone is in excess with respect to the Me oxide or hydroxide.
  • the acetylacetone / oxide or hydroxide molar ratio of Me is greater than 2 when the oxide or hydroxide of Me is divalent and greater than 3 when the oxide or hydroxide of Me is trivalent, more preferably greater than or equal to 4 when the oxide or hydroxide of Me is divalent and greater than or equal to 6 when the oxide or hydroxide of Me is trivalent, more preferably equal to 6 when the oxide or hydroxide of Me is divalent and equal to 9 when the oxide or hydroxide of Me is trivalent.
  • AAH represents acetylacetone in enol form.
  • the reaction time is generally between 2h and 6h, preferably of the order of 4h.
  • a filtration step is generally carried out to recover a solid phase comprising Me hydrated acetylacetonate and a liquid filtrate comprising water, acetylacetone in excess and a Me acetylacetonate hydrate fraction. solubilized.
  • the liquid filtrate must be homogeneous, that is to say, have only one phase.
  • the weight of acetylacetone in the aqueous phase of the liquid filtrate must advantageously remain less than or equal to 15% of the weight of the aqueous phase. Beyond this, filtration is more difficult and recycling must take into account that the filtrate can be biphasic.
  • the aqueous dilution of the initial reaction medium (Me oxide or hydroxide and acetylacetone in water) must be adapted accordingly.
  • the Me acetylacetonate present in the solid phase is in a hydrated form. It is then usually dried.
  • This drying can be carried out by applying a vacuum and / or reducing the vapor pressure by a flow of gas, preferably inert, and / or by increasing the temperature of the product to remove the free water (obtaining the dried hydrated product), and also the water of crystallization in the case of an anhydrous end product.
  • the drying temperature is generally less than 75 ° C.
  • the drying temperature is generally below 65 ° C.
  • the product obtained, hydrated or anhydrous Me acetylacetonate, is in the form of a powder of fine non-agglomerated particles.
  • This recovered product is very pure, with a purity close to 100%, and requires no washing because there is no secondary reaction product (such as sodium chloride).
  • the liquid filtrate obtained at the end of the filtering stage is advantageously entirely recycled for the following synthesis as well as the vapors obtained at the end of the drying. This recycling operation is repeated at each new synthesis so that there is no loss of chemical element Me or acetylacetone.
  • the condensates obtained during the drying step essentially contain water and a little acetylacetone. In an industrial implementation, they can advantageously be fully recycled in the following syntheses.
  • the subject of the invention is also a batch continuous process for the synthesis of acetylacetonate of a hydrated or anhydrous Me chemical element, in which the chemical element Me is chosen from alkaline earth metals, transition metals and lanthanides, said process comprising n successive steps of reaction in an aqueous medium of the oxide or hydroxide of Me introduced in solid form and acetylacetone, the acetylacetone being in excess relative to the oxide or hydroxide of Me, a filtration being carried out at the end of each reaction i, i ranging from 1 to n, the liquid filtrate recovered at the end of the reaction i ', i' varying from 1 to n-1, and comprising water, acetylacetone in excess and a solubilized hydrated Me acetylacetonate fraction, being recycled by adding to the reaction medium of the reaction i '+ 1, n being greater than or equal to 2.
  • batch continuous process is meant in the sense of the present invention a process comprising
  • alkaline earth metals that can be used according to the invention, mention may be made of magnesium, calcium, strontium and barium.
  • the chemical element Me is preferably chosen from cobalt, magnesium, nickel, calcium, neodymium and zinc.
  • n ranges from 2 to 60, more preferably from 2 to 40, more preferably from 2 to 20.
  • the acetylacetone / oxide or hydroxide molar ratio of Me is greater than 2 when the oxide or hydroxide of Me is divalent and greater than 3 when the oxide or hydroxide of Me is trivalent, preferably greater than or equal to 4 when the oxide or hydroxide of Me is divalent and greater than or equal to 6 when the oxide or hydroxide of Me is trivalent, more preferably equal to 6 when the oxide or hydroxide of Me is divalent and equal to 9 when the oxide or Me hydroxide is trivalent.
  • Filtration is carried out after each reaction i. Filtration makes it possible to recover acetylacetonate from the chemical element
  • the weight of acetylacetone in the aqueous phase of the liquid filtrate is less than or equal to 15% of the weight of the aqueous phase.
  • the continuous batch process according to the invention thus makes it possible to recycle the filtrate of each synthesis reaction of the Me acetylacetonate hydrate in the following reaction.
  • the yield is thus quasi-quantitative.
  • the process does not require specific treatment of waste effluents.
  • the acetylacetonate of the hydrated Me chemical element recovered after filtration after each reaction is preferably dried.
  • the invention further relates to a process for the preparation of acetylacetonate of a hydrated or anhydrous Me chemical element, wherein the chemical element Me is selected from alkaline earth metals, transition metals and lanthanides, from of Me oxide or hydroxide and acetylacetone, wherein said Me acetylacetonate is obtained as well as a liquid filtrate containing acetylacetone in aqueous phase and a condensate, the liquid filtrate being capable of being used for a new acetylacetonate preparation of the Me element as a reagent.
  • the chemical element Me is selected from alkaline earth metals, transition metals and lanthanides, from of Me oxide or hydroxide and acetylacetone, wherein said Me acetylacetonate is obtained as well as a liquid filtrate containing acetylacetone in aqueous phase and a condensate, the liquid filtrate being capable of being used for a new acety
  • said process comprises a first step of reaction in an aqueous medium of the oxide or hydroxide of the element Me introduced in solid form and acetylacetone, the acetylacetone being in excess relative to the oxide or the Me hydroxide, and a second filtration step.
  • the weight of acetylacetone in the aqueous phase of the liquid filtrate is advantageously less than or equal to 15% of the weight of the aqueous phase.
  • the condensate may be used for a new acetylacetonate preparation of the Me element as a reagent.
  • magnesium contained in magnesium acetylacetonate is released in the aqueous phase by dissolving with acetone and then hydrolysed with a hydrochloric acid solution.
  • the manipulation consists in a determination of the magnesium ions (Mg2 +) of the sample by EDTA in the presence of a colored indicator: the Black Eriochrome T (denoted NET).
  • the end of dosing detection is performed by a phototrode set at 660nm.
  • the magnesium ions preferentially complex with EDTA. At the end of the assay, all magnesium ions will have complexed with EDTA.
  • the colored indicator (NET) will resume its free form and initial color: bluish. This color change is followed by the phototrode mentioned above.
  • the hydrotimetric titer is the amount of EDTA (noted as H2Y2-) used to reach the turn.
  • cobalt contained in cobalt acetylacetonate is released in aqueous phase by dissolution in acetone and then hydrolysed with a hydrochloric acid solution.
  • the manipulation consists of a determination of the cobalt ions of the sample by EDTA in the presence of a colored indicator: orange xylenol. End-of-dosing detection is performed by visual observation of a color change.
  • Cobalt ions preferentially complex with EDTA. At the end of the assay, all cobalt ions will have complexed with EDTA.
  • the colored indicator (orange xylenol) will resume its free form and its initial color: orange. This color change is followed visually.
  • the hydrotimetric titer is the amount of EDTA (noted as H2Y2-) used to reach the turn.
  • Mg level by spectrophotometry in magnesium acetylacetonate Magnesium acetylacetonate is hydrolysed in an acidified aqueous solution (for example with hydrochloric acid) while hot. Once the complete dissolution of the magnesium acetylacetonate has been achieved, the solution thus obtained is analyzed by ICP (Inductively Coupled Plasma) coupled to a spectrophotometric atomic emission detector (AES). When introduced into the ICP-AES elements present in the solution will be excited in contact with the plasma. When they return to their ground state, they will emit radiation whose wavelength is representative of their chemical nature. Thus, by detecting the intensity of the radiation at the wavelength corresponding to magnesium, it will be possible to determine the content within the solution.
  • ICP Inductively Coupled Plasma
  • AES spectrophotometric atomic emission detector
  • Cobalt acetylacetonate is hydrolysed in an acidified aqueous solution (for example with nitric acid).
  • an acidified aqueous solution for example with nitric acid.
  • ICP Inductively Coupled Plasma
  • AES spectrophotometric atomic emission detector
  • the initial aqueous dilution is advantageously calculated so as to keep a homogeneous aqueous phase for the filtrate. This limit is reached when the weight of acetylacetone in water approaches 15%. When this limit is exceeded, a supernatant organic phase will appear in the filtrate. This situation can make filtration more difficult.
  • the experimental conditions are as follows:
  • the hydroxide of Mg is completely added to the filtrate of reaction 1 (first without stirring) and then acetylacetone and the balance of water (correction of the loss due to drying since in this example it is not There is no recycling of the condensate) are added with stirring in this suspension.
  • the reaction time is 4 hours.
  • Acetylacetone and the balance of water are added to the filtrate of reaction 2 with stirring (the inverse, namely the filtrate in acetylacetone and additional water is also possible).
  • the hydroxide of Mg is added in small portions in the water-acetylacetone reaction medium (slightly biphasic but well stirred at ⁇ 500tr / min).
  • the addition (spatulate) lasts between l 0-15 min.
  • the total reaction time (4h) includes this addition time.
  • the magnesium acetylacetonate obtained is dried to obtain either an anhydrous form or a dihydrate form with the latter less severe drying conditions.
  • the drying conditions in an oven are a temperature of 50 ° C. under vacuum of approximately 60 mbar. regulated with a slight nitrogen sweep, until a constant mass is obtained.
  • the drying conditions in an oven are a temperature of 50 ° C under vacuum of about 500 mbar regulated with a slight nitrogen sweep, until a constant mass is obtained.
  • the yield of magnesium acetylacetonate (anhydrous or dihydrate) calculated from the amount of the introduced magnesium hydroxide is given for each reaction in Table 2. For example, the yield for reaction 7 is 96% (79%). 5 g of product obtained) if it is considered that the product is in the dihydrate form (258.55 g / mol). The theoretical rate of magnesium is 9.40%. This yield illustrates the loss of magnesium acetylacetonate by solubilization in the filtrates and the interest of recovering these filtrates. Table 2
  • the aqueous filtrate containing the excess of acetylacetone and solubilized cobalt acetylacetonate is entirely recycled in a following synthesis.
  • the operation is repeated 3 times.
  • the initial aqueous dilution is advantageously calculated so as to keep a homogeneous aqueous phase for the filtrate. This limit is reached when the weight of acetylacetone in water approaches 15%. When this limit is exceeded a supernatant organic phase will appear in the filtrate. This situation can make filtration more difficult.
  • the experimental conditions are as follows: Reaction 1:
  • the Co (II) hydroxide is totally added to the filtrate of reaction 1 (suspension with stirring) and then acetylacetone and the addition of water (correction of the loss due to drying in that in this case example there is no recycling of condensate) are added with stirring in this suspension.
  • the reaction time is 4 hours at room temperature with stirring ( ⁇ 500 rpm).
  • the cobalt acetylacetonate obtained is dried to obtain an anhydrous form.
  • the drying conditions in an oven are a temperature of 50 ° C under vacuum of about 250 mbar regulated with a slight sweep of air or nitrogen) to a constant mass.
  • the color of the product obtained shows that the product obtained is the acetylacetonate cobalt dihydrate.
  • the yield of cobalt (II) acetylacetonate calculated from the amount of cobalt (II) hydroxide introduced is given for each reaction in Table 4. For example, the yield for reaction 3 is 97% (91%). g of product obtained) if it is considered that the product is in the dihydrate form (293.18 g / mol). The theoretical cobalt level is 20, 10%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Catalysts (AREA)
EP19735369.1A 2018-06-05 2019-06-05 Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre Pending EP3802477A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1854881A FR3081868B1 (fr) 2018-06-05 2018-06-05 Procede de preparation de l'acetylacetonate d'un element chimique hydrate ou anhydre
PCT/FR2019/051345 WO2019234356A1 (fr) 2018-06-05 2019-06-05 Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre

Publications (1)

Publication Number Publication Date
EP3802477A1 true EP3802477A1 (fr) 2021-04-14

Family

ID=63080140

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19735369.1A Pending EP3802477A1 (fr) 2018-06-05 2019-06-05 Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre

Country Status (5)

Country Link
US (1) US20210238118A1 (ko)
EP (1) EP3802477A1 (ko)
KR (1) KR20210018258A (ko)
FR (1) FR3081868B1 (ko)
WO (1) WO2019234356A1 (ko)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114394889A (zh) * 2021-12-20 2022-04-26 西安凯立新材料股份有限公司 一种三乙酰丙酮铑的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3474464A (en) * 1967-08-03 1969-10-21 Grace W R & Co Process for preparing acetylacetonates
DE2420775C3 (de) * 1974-04-29 1980-01-31 Wacker-Chemie Gmbh, 8000 Muenchen Verfahren zur Herstellung von Mangan (Ill)acetylacetonat
WO1989007666A1 (en) * 1988-02-19 1989-08-24 Northwestern University Method of forming superconducting materials
DE19610320C2 (de) 1996-03-15 1998-01-22 Henkel Kgaa Verfahren zur Herstellung von Erdalkalimetallsalzen aliphatischer beta-Ketoverbindungen
JP2000026362A (ja) 1998-07-10 2000-01-25 Daicel Chem Ind Ltd β−ジケト化合物のアルカリ土類金属塩の製造方法
WO2004056737A1 (en) * 2002-12-23 2004-07-08 Council Of Scientific And Industrial Research Process for the preparation of metal acetylacetonates
CN1313473C (zh) * 2005-05-19 2007-05-02 北京化工大学 一种乙酰丙酮钴的制备方法
US7442820B1 (en) * 2008-01-25 2008-10-28 W.C. Heraeus Gmbh Process for the preparation of platinum acetylacetonato complexes

Also Published As

Publication number Publication date
WO2019234356A1 (fr) 2019-12-12
FR3081868A1 (fr) 2019-12-06
US20210238118A1 (en) 2021-08-05
FR3081868B1 (fr) 2020-11-06
KR20210018258A (ko) 2021-02-17

Similar Documents

Publication Publication Date Title
EP0486351B1 (fr) Procédé de fabrication d'oxalates doubles de terres rares et d'ammonium et leurs utilisations pour la fabrication d'oxydes de terres rares
FR2537558A1 (fr) Procede pour la fabrication d'apatite
EP3802477A1 (fr) Procédé de préparation de l'acétylacétonate d'un élément chimique hydraté ou anhydre
Morais et al. Recovery of europium from a rare earth chloride solution
JP2002543174A (ja) １級アルコールからのカルボン酸塩の製造方法
EP2821393B1 (fr) Procédé de synthèse de composés azo
JPH05255713A (ja) 銅粉末の製法
CA2019489A1 (fr) Melanges deshydrates d'halogenures de terres rares et d'alcalino-terreux ou d'alcalins
EP0208581B1 (fr) Nouveau composé de cérium IV et son procédé de préparation
JPH10216742A (ja) 重金属含有イオンの捕集方法
EP0673879B1 (fr) Procédé de préparation de sels de calcium à faible teneur en aluminium
JP3503116B2 (ja) 高濃度フリーヒドロキシルアミン水溶液の製造法
EP0053532B1 (fr) Procédé pour la préparation de catalyseurs à base d'oxydes de molybdène et/ou de tungstène et d'oxydes d'autres métaux
EP3904329A1 (en) Process for hydrodefluorination of aromatic trifluoromethyl derivatives
FR1464433A (fr) Procédé de préparation d'un luminophore
CA1212514A (fr) Sulfate cerique tres soluble
EP1086953B1 (fr) Procédé de purification de la diosmine
JP7265851B2 (ja) 炭酸銀製造方法
JP2000007331A (ja) セリウムの回収方法
RU2161123C1 (ru) Способ получения окисленного графита
JPS6148506A (ja) 気相法微粒子の精製方法
JP2003267726A (ja) 精製塩化第一銅の製造方法
JPH04317419A (ja) 臭化マンガン水溶液の製造方法
FR2516657A1 (fr) Procede pour la mise en evidence et l'elimination d'ions de metaux de transition labiles de substitution
WO1993014031A1 (fr) Preparation et application de composes bromes du manganese

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210111

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)