[go: up one dir, main page]

WO2001092196A1 - Procede de fabrication d'acides poly- ou monomethylolalcanoiques - Google Patents

Procede de fabrication d'acides poly- ou monomethylolalcanoiques Download PDF

Info

Publication number
WO2001092196A1
WO2001092196A1 PCT/EP2001/005817 EP0105817W WO0192196A1 WO 2001092196 A1 WO2001092196 A1 WO 2001092196A1 EP 0105817 W EP0105817 W EP 0105817W WO 0192196 A1 WO0192196 A1 WO 0192196A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
hydrogen peroxide
phase
temperature
weight
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.)
Ceased
Application number
PCT/EP2001/005817
Other languages
German (de)
English (en)
Inventor
Hagen Weigl
Klaus Ebel
Gisela Hieber
Gerhard Schulz
Carsten GRÖNING
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2001092196A1 publication Critical patent/WO2001092196A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds

Definitions

  • the invention relates to a process for the preparation of poly- or monomethylolalkanoic acids, in particular dimethylolalkanoic acids.
  • Chemical abstract 131: 20530 discloses from Pige Huagong (1998), 15 (6), 27-29, a technical report by the Institute of Applied Chemistry at the University of Anhui in Hefei, People's Republic of China, which describes the production of dimethylolpropionic acid by oxidation of dimethylolpropanal using HO 2 .
  • H 2 O 2 is added to dimethylolpropanal at 50 to 60 ° C. and the resulting reaction mixture is gradually heated to 95 ° C.
  • the present invention was therefore based on the object of providing a process for the preparation of polymethylolalkanoic acids or monomethylolalkanoic acids with which the selectivity can be increased significantly in order to reduce the proportion of by-products and the yield of the desired polymethylolalkanoic acid or monomethylolalkanoic acid to increase.
  • R can be identical or different and represents a substituted or unsubstituted aliphatic hydrocarbon or a methylol group, from the corresponding poly- or monomethylolalkanals of the general formula (II)
  • the initial phase of the reaction means at least the reaction time required for metering the hydrogen peroxide to the alkanal.
  • the initial phase is defined such that it comprises at least the time in which the components are metered in, the initial phase comprising at least about 1% of the reaction or residence time of the reaction mixture.
  • the end phase is understood to mean the reaction or residence time in which the reaction components are mixed in the desired ratio and at a higher temperature than in the initial phase, i.e. be allowed to continue reacting at a temperature above 85 ° C.
  • the process for the preparation of the polymethylolalkanoic acids can be carried out by reacting the polymethylolalkanals required as starting compounds as pure substance or in a mixture with other compounds. Since the corresponding polymethylolalkanals are produced, for example, by aldol reaction of the corresponding aliphatic aldehydes with formaldehyde in the presence of a basic catalyst, the reaction product can also be fed directly to the oxidation reaction to the polymethylolalkanoic acid in this reaction. Partial or complete purification beforehand is possible, but not absolutely necessary. Such purification can be carried out, for example, as indicated in German patent application No. 199 63 445.9.
  • the reaction proceeds more selectively than in the reaction procedures known in the prior art. Due to a reaction temperature of at least ⁇ 40 ° C and preferably ⁇ 60 ° C during the initial phase, the reaction with hydrogen peroxide also takes place more quickly and an accumulation is counteracted, so that the reaction according to the invention also brings safety-related advantages.
  • evaporative cooling can be achieved at this initial temperature even at a lower negative pressure, which can be advantageously used for carrying out the reaction.
  • the evaporation enthalpy of the solvent can be used to dissipate the high heat of reaction, which enables faster dosing and can be used independently of other heat exchangers.
  • solvents can be removed without additional energy expenditure.
  • the reaction temperature during the initial phase must also not be chosen too high, since hydrogen peroxide is decomposed at temperatures of> 95 ° C. without causing the desired oxidation reaction.
  • the reaction temperature is> 85 to 110 ° C, preferably> 85 to 105 ° C.
  • the change of temperatures between the beginning and the end phase can take place as quickly as possible.
  • the process is in principle suitable for the production of poly- or monomethylolalkanoic acids, it preferably relates to the production of dimethylolalkanoic acids from the corresponding dimethylolalkanals.
  • Dimethylolalkanoic acids or dimethylolalkanals in which the aliphatic hydrocarbon radical R has 1 to 5 carbon atoms are to be mentioned in particular.
  • Those dimethylolalkanals are particularly preferred as starting compounds to be oxidized, the aliphatic radical of which has one or two carbon atoms, which is then dimethylolbutanal or dimethylolpropanal.
  • An aqueous solution of hydrogen peroxide is used as the oxidizing agent, with a content of 5 to 60%, preferably 30 to 50%, of hydrogen peroxide.
  • This concentration range advantageously provides a minimum amount of oxidizing agent per unit volume of solvent. It has been shown that too much water present at the end of the reaction greatly hinders subsequent work-up, owing to the high solubility of the desired end product, and even a further work-up step, e.g. Evaporation may require. On the other hand, it has also been shown that too high concentrations of hydrogen peroxide, i.e. Concentrations above 60% are not very advantageous because the hydrogen peroxide then tends to decompose.
  • the stoichiometric ratios ie the ratio of hydrogen peroxide added as the oxidizing agent to the compound to be oxidized
  • compliance with a defined stoichiometric ratio has a significant effect on the yield.
  • the significantly higher selectivity which is achieved in the reaction carried out according to the invention is also due to the changed stoichiometric ratio calculation compared to the prior art.
  • the amount of formaldehyde and dimethylolpropionaldehyde in the reaction solution at the beginning of the oxidation reaction is in principle used to calculate the stoichiometric ratio.
  • the ratio of the hydrogen peroxide used to the sum of these aldehydic compounds mentioned is, according to the invention, 0.5 to 0.99, preferably 0.7 to 0.99, particularly preferably 0.85 to 0.95. That the oxidizing agent is used sub-stoichiometrically to the amount of the compounds to be oxidized.
  • the process according to the invention enables the polymethylolalkanoic acids to be prepared with a purity of> 96%. These are then obtained by crystallization from the reaction mixture, solid / liquid separation and subsequent washing with water or another suitable solvent or solvent mixture in the stated purity, without further purification steps, e.g. Extraction, going through an ion exchanger or the like would be necessary. As a result, the process according to the invention is less complex and does not provide any salt accumulation when regenerating an ion exchanger used for cleaning purposes. Buffering of the reaction solution is also not necessary in the present process.
  • the resulting filtrate from the solid / liquid separation can be further concentrated by removing the distillate at normal pressure or under reduced pressure, so that the corresponding polymethylolalkanoic acid crystallizes again when it cools down. will hold.
  • This can be separated from the mother liquor by solid / liquid separation.
  • the mother liquor obtained in this way can in turn be concentrated and processed further.
  • the purity of the crystals can be increased by washing or recrystallizing. However, cleaning can also be dispensed with and the crystals can be returned to the next reaction run before crystallization. This achieves a cleaning effect without having to provide an additional procedural step.
  • wash water of the first crystals which may still contain the end product due to the partially high solubility of the polymethlolalkanoic acids, can be returned to the next run.
  • the solvent which is returned at the same time as the end product can then be removed by distillation at normal pressure or in vacuo.
  • the mother liquor obtained through a single or repeated reprocessing has a significantly lower water content. Therefore, the disposal will be done more cost-effectively by incineration, since less water "must be heated and vaporized.
  • Example 2 the oxidation was carried out without temperature grading, i.e. the temperature remained the same during the initial and final phases.
  • the temperature was varied in order to show the influence of this reaction parameter on the yield or the selectivity of the reaction.
  • Examples 4 and 6 were also carried out without staggering the temperature, but with a reaction temperature which was higher than in Example 2, which is in the region of the temperature during the final phase of the process according to the invention, and with a reaction time which was longer than in Example 2.
  • the further examples 7-10 relate to process procedures according to the invention. Table 1 gives an overview of the reaction parameters and results.
  • Example 4 The reaction was carried out as described in Example 2, but after a reaction time of 4 hours the temperature was raised to reflux (at atmospheric pressure) and held for 2 hours. The turnover was then 97.2%. The yield in the solution was 80.7%, the selectivity was 82%.
  • Example 4 The reaction was carried out as described in Example 2, but after a reaction time of 4 hours the temperature was raised to reflux (at atmospheric pressure) and held for 2 hours. The turnover was then 97.2%. The yield in the solution was 80.7%, the selectivity was 82%.
  • the reaction was carried out as described in Example 4, but after a reaction time of 4 h, the temperature was raised to reflux (at atmospheric pressure) and held for 2 h. The turnover was then 97.5%. The yield in the solution was 75.3%, the selectivity was 77%.
  • heating interval dwell time in the final phase

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de fabrication d'acides poly- ou monométhylolalcanoïques de formule générale (I) dans laquelle R peut être identique ou différent et désigne un hydrocarbure aliphatique substitué ou non substitué ou un groupe méthylol, à partir des poly- ou monométhylolalcanals correspondants de formule générale (II) où R a la signification précitée, par oxydation au moyen de peroxyde d'hydrogène. Il importe de différencier une phase initiale et une phase finale de la réaction, la température de réaction choisie durant la phase initiale étant plus faible que celle choisie durant la phase finale et étant au moins >/= 40 DEG C à 85 DEG C, de préférence de 60 à 80 DEG C, au mieux, de 65-75 DEG C, la température durant la phase finale étant > 85 DEG C-110 DEG C, et s'élevant de préférence jusqu'à 105 DEG . Le procédé est utilisé notamment pour la production d'acides diméthylolalcanoïques à partir des diméthylolalcanals correspondants, en particulier pour la production de diméthylolbutanal ou de diméthylolpropanal.
PCT/EP2001/005817 2000-05-26 2001-05-21 Procede de fabrication d'acides poly- ou monomethylolalcanoiques Ceased WO2001092196A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2000126141 DE10026141A1 (de) 2000-05-26 2000-05-26 Verfahren zur Herstellung von Poly- oder Monomethylolalkansäuren
DE10026141.8 2000-05-26

Publications (1)

Publication Number Publication Date
WO2001092196A1 true WO2001092196A1 (fr) 2001-12-06

Family

ID=7643674

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2001/005817 Ceased WO2001092196A1 (fr) 2000-05-26 2001-05-21 Procede de fabrication d'acides poly- ou monomethylolalcanoiques

Country Status (2)

Country Link
DE (1) DE10026141A1 (fr)
WO (1) WO2001092196A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312736A (en) * 1963-07-29 1967-04-04 Trojan Powder Co Method of making polymethylol-alkanoic acids
US5801276A (en) * 1996-08-16 1998-09-01 Bayer Aktiengesellschaft Process for the preparation of hydroxypivalic acid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3312736A (en) * 1963-07-29 1967-04-04 Trojan Powder Co Method of making polymethylol-alkanoic acids
US5801276A (en) * 1996-08-16 1998-09-01 Bayer Aktiengesellschaft Process for the preparation of hydroxypivalic acid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; KO, KEIUN ET AL.: "2,2-Dimethyl-3-hydroxypropionic acid", XP002175368, Database accession no. 71:30073 *
DATABASE CHEMABS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; ZHAO, XIAOPING ET AL.: "Synthesis of 2,2-dimethylolpropionic acid (DMPA)", XP002175367, Database accession no. 131:20530 *
PIGE HUAGONG, vol. 15, no. 6, 1998, pages 27 - 9 *

Also Published As

Publication number Publication date
DE10026141A1 (de) 2001-11-29

Similar Documents

Publication Publication Date Title
DE1695753C3 (de) Verfahren zur Herstellung von 6,6disubstituierten 2,2-Dimethyl-4-oxopiperidinen
DE2207699A1 (fr)
DE10215943B4 (de) Aufarbeitung von Rückständen bei der Herstellung von Carbonsäuren
CH635308A5 (de) Verfahren zur denitrosierung von n-nitrosoverbindungen.
DE69901519T2 (de) Verfahren zur Herstellung von 2,2'-bis (Hydroxymethyl)alkansäure
DE2548470C2 (de) Verfahren zur Herstellung von reinem 2,2-Bis-(4-hydroxyphenyl)-propan
DE2517054A1 (de) Verfahren zur herstellung von nicotinsaeureamid
EP1955994B1 (fr) Procédé destiné à la fabrication de DMA
DE2919974A1 (de) Verfahren zur herstellung von cyanhydrinacylaten von aldehyden
WO2002038527A1 (fr) Procede de production d'acides d'alcane de polymethylol ou d'alcane de monomethylol
DE3729471C2 (fr)
WO2001092196A1 (fr) Procede de fabrication d'acides poly- ou monomethylolalcanoiques
DE1256210B (de) Verfahren zur Reinigung von Terephthalsaeure
DE1643083C3 (fr)
DE2111196A1 (de) Verfahren zur Gewinnung von Adipinsaeure
DE930204C (de) Verfahren zur Herstellung von Pentaerythrit
DE2729627C2 (de) Verfahren zur Herstellung von farblosen, als Weichmacher verwendbaren Carbonsäureestern
DE2540726C3 (de) Verfahren zur Gewinnung reiner Diglykolsäure aus dem durch Oxidation von Diäthylenglykol mit Salpetersäure erhaltenen Reaktionsgemisch
WO2001090040A2 (fr) Procede pour isoler des acides polymethylolalcaniques et pour eliminer les courants de rebut resultant de ce procede
DE2459233C2 (de) Verfahren zur Herstellung von Hydrochinon
DE2410988C3 (de) Verfahren zur Herstellung von 2-Aminobutanol
DE2408948C3 (de) Kontinuierliches Verfahren zur Gewinnung von Glycid
DE10232812A1 (de) Verbessertes Verfahren zur Reinigung von Poly- und Monomethylolalkansäure
CH644576A5 (de) Verfahren zur herstellung von anisaldehyd.
DE2307310B2 (de) Verfahren zur Abtrennung von Diaminomaleonitril aus einem bei der katalytischen Tetramerisierung von Cyanwasserstoff erhaltenen Reaktionsgemisch

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP