EP2076505A1 - Verfahren für die synthese zyklischer acetale mittels reaktiver extraktion eines polyols in einer konzentrierten lösung - Google Patents

Verfahren für die synthese zyklischer acetale mittels reaktiver extraktion eines polyols in einer konzentrierten lösung

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Publication number
EP2076505A1
EP2076505A1 EP07858522A EP07858522A EP2076505A1 EP 2076505 A1 EP2076505 A1 EP 2076505A1 EP 07858522 A EP07858522 A EP 07858522A EP 07858522 A EP07858522 A EP 07858522A EP 2076505 A1 EP2076505 A1 EP 2076505A1
Authority
EP
European Patent Office
Prior art keywords
acid
glycerol
polyol
cyclic
acetals
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.)
Withdrawn
Application number
EP07858522A
Other languages
English (en)
French (fr)
Inventor
Jean-Luc Dubois
Sara Iborra Chornet
Alexandra I. Lucienne Velty
Avelino Corma Canos
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.)
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
Original Assignee
Consejo Superior de Investigaciones Cientificas CSIC
Universidad Politecnica de Valencia
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Filing date
Publication date
Application filed by Consejo Superior de Investigaciones Cientificas CSIC, Universidad Politecnica de Valencia filed Critical Consejo Superior de Investigaciones Cientificas CSIC
Publication of EP2076505A1 publication Critical patent/EP2076505A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
    • C07D317/20—Free hydroxyl or mercaptan
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
    • C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings

Definitions

  • the present invention relates to a process for synthesizing cyclic acetals by reactively extracting a polyol contained in an aqueous phase by reaction of an aldehyde and / or a ketone on the polyol leading to the formation of a cyclic acetal of polyol insoluble in the aqueous phase.
  • the process of the invention consists in reacting at least one aldehyde and / or a ketone, or more generally a carbonyl compound, with a polyol contained in a polyol-rich aqueous phase, in a reactor comprising an acid catalyst which makes it possible simultaneously to carry out the catalytic conversion of the reactants and the separation of the products of the reaction by extraction of the polyol from the aqueous phase in the form of a cyclic acetal insoluble in the aqueous phase.
  • the synthesis of acetals is largely described in the article by F. A. J.
  • the cyclic acetals produced in the process of the invention are formed by simultaneous reaction of the aldehyde and / or the ketone on two hydroxyl functions of the polyol.
  • the proximity of the two hydroxyl functions results in the formation of a ring comprising in general, but not exclusively, 5 to 6 atoms including 2 oxygen.
  • This reaction is a balanced and reversible reaction and is accompanied by water formation.
  • the reaction carried out in the process with glycerol as polyol and under acid catalysis is as follows: (1) in which the radicals R 1 and R 2 are especially alkyl radicals and can also be hydrogen.
  • Cyclic glycerol acetals can be synthesized according to many methods known from the literature. For example:
  • acetal glycerol and acetone (RN 100-79-8) is also known as Solketal. It is a solvent whose boiling point is 188-189 ° C (and 82 ° C to 10 mmHg), the melting point is -26.4 ° C, and flash point
  • Formal Glycerol is another glycerol acetal that is commercially available from Lambiotte. There exist in the form of 2 isomers, dioxane (ring with 6 atoms) and dioxolane (cycle with 5 atoms). The physico-chemical characteristics of this acetal, which is miscible with water, are available on the site www.Lambiotte.com.
  • Patent FR 2869232 relates to new pharmaceutical or cosmetic excipients based on cyclic acetals including glycerol acetals.
  • methods for synthesizing acetals obtained from propanaldehyde, butyraldehyde and pentanal are exemplified. It is recommended in this patent to use light aldehydes to maintain in the aqueous phase the aldehyde and acetal product.
  • US patent application 5917059 describes a method for synthesizing light glycerol acetals by continuously distilling an excess of aldehyde or ketone resulting in the water produced by the reaction and by continuous supply of the aldehyde or ketone containing less than 1% water.
  • an aqueous solution of glycerol containing from 30 to 80% by weight of glycerol, or of glycerol hydrate containing from 20 to 1% by weight of water (ie from 80 to 99% by weight of glycerol), is placed in contact with an aldehyde or ketone, in the presence of an acid catalyst, in a solvent having a boiling point generally below 150 ° C. and having a boiling point lower than that of the aldehyde or ketone, and the role is the elimination of the water present in the medium, originating from either the initial solution or the reaction, by azeotropic distillation.
  • the object of the invention is to provide a process for the continuous industrial production of cyclic acetals by extraction of polyols and in particular glycerol contained in aqueous solutions which does not have the disadvantages of the aforementioned methods.
  • the invention relates to a process for synthesizing cyclic acetals by reacting at least one carbonyl-functional compound chosen from aldehydes, ketones and / or linear acetals on a polyol in concentrated aqueous solution, characterized in that is carried out in a reactor containing an acid catalyst and that the carbonyl compound is selected such that the cyclic acetal produced has a solubility in water of less than 20,000 mg / kg at room temperature and that simultaneously in the catalytic synthesis reaction of the cyclic acetal, at least a portion of the organic phase containing the cyclic acetal is removed by extraction within the reactor from the aqueous continuous phase.
  • the invention relates to a process for synthesizing cyclic acetals from concentrated solutions of polyols, that is to say solutions initially containing at least 20% by weight of polyol in water, and preferably more than 40%. weight.
  • the high content of polyols which constitutes an excess of polyol reagent will allow a total conversion of the other reagent, the carbonyl compound and in particular the aldehyde and / or the ketone within the reactor.
  • polyols that can be used in the process of the invention, mention may be made of: glycerol, ethylene glycol, propane diol 1, 2 and / or propane diol 1, 3, butanediol 2,3.
  • aldehydes that can be used in the process of the invention mention may be made of: butyraldehyde, n-heptanaldehyde, 2-ethylhexanaldehyde, valeraldehyde, glyoxal, glutaraldehyde, furfuraldehyde, isovaleraldehyde, acrolein, crotonaldehyde, decanaldehyde, 2-ethylbutaraldehyde, hexanaldehyde, isobutyraldehyde, isodecanaldehyde, laurinaldehyde, 2-methylbutyraldehyde, nonanaldehyde, octanaldehyde, pivalaldehyde, tolualdehyde, benzaldehyde, tridecanaldehyde, undecanaldehyde.
  • ketones that can be used in the process of the invention, mention may notably be made of: acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diisobutyl ketone, diisopropyl ketone, mesityl oxide, butanedione, cyclohexanone.
  • the data relating to the solubilities in water of chemical compounds are provided in particular in: Yaws' Handbook of Thermodynamics and Physical Properties of Chemical Compounds ⁇ 2003 Knovel.
  • the aldehydes or ketones selected are generally taken from aldehydes and ketones comprising from 4 to 12 carbon atoms, and even more preferably from 5 to 9.
  • aldehydes and ketones that are particularly suitable for the process of the invention, mention may be made of aldehydes, benzaldehyde (6570 mg / kg), heptanals and in particular n-heptanal (1516 mg / kg), hexanal (5644 mg / kg), pentanal (11,700 mg / kg), n-heptanal, octanol (370 mg / kg); for ketones mention may be made of acetophenone (6842 mg / kg), benzophenone (136.7 mg / kg), diisobutyl ketone (2640 mg / kg) and diisopropyl ketone (5700 mg / kg).
  • heptanaldehyde (n-heptanal), since this aldehyde can be obtained from biomass.
  • Heptanaldehyde is obtained, for example, by thermal cracking of the methyl ester of castor oil.
  • acetals may be selected from light alcohols and heavy aldehydes to produce poorly soluble acetals in water.
  • the light alcohols can be selected from methanol, ethanol, propanol
  • heavy aldehydes can be the same as those mentioned above.
  • linear acetals that may be used in the process according to the invention, mention may be made in particular of: malonaldehyde bis (diethyl acetal) (CAS RN 122-31-6), 1,1-diethoxycyclohexane (CAS RN 1670-47-9 ), 1,4-cyclohexadione bis (ethylene acetal) (CAS RN 183-97-1), phenylacetaldehyde dimethyl acetal (CAS RN 101-48-4), benzaldehyde dimethyl acetal (CAS RN 1125-88-8), 1,1-dimethoxyheptanalacetal (CAS RN 10032-55-0), 1,1-dimethylhexanalacetal (CAS RN 1599-47-9).
  • malonaldehyde bis diethyl acetal
  • 1,1-diethoxycyclohexane CAS RN 1670-47-9
  • 1,4-cyclohexadione bis ethylene acetal
  • the catalyst of the reaction is an acid catalyst which is either in solid form, heterogeneous catalysis or in liquid form, homogeneous catalysis.
  • the reactor is a stirred reactor in the case of homogeneous catalysis.
  • the liquid catalyst is selected from those catalysing the reaction between an alcohol and an aldehyde or a ketone.
  • acidic liquids that may be used as catalysts, mention may be made of: hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, para-toluenesulfonic acid, triflic acid, acid oxalic, etc.
  • the soluble acids are preferably selected in the aqueous phase.
  • the acidic solids that may be used as catalysts, mention may be made of acidic ion exchange resins, acid resins, natural or synthetic zeolites such as mordenite, Y zeolites, ZSM5, H-beta, Montmorillonite or silica-based silicones. aluminas, Nafion ® composites and Nafion ® or finally supported heteropolyacids, chlorides of lanthanides, iron, zinc or titanium or the catalysts contained in the list given in the article by FAJ Meskens cited above.
  • the acidic catalyst consists of an acidic phase having a Hammett acidity H 0 of less than +2, preferably less than 0.
  • the typical acidic acid Hammett acidities are grouped together. in the table below
  • Hammett acidity for a solid is defined in the article by K. Tanabe et al in "Studies in Surface Science and Catalysis", Vol 51, 1989, Chapters 1 and 2.
  • Hammett's acidity is determined by amino titration using indicators or adsorbing a base in the gas phase.
  • Hammett's acidity is one of many scales of acidity in solids. There are correlations in the literature between different scales of acidity.
  • Acidic solids which may be suitable are natural or synthetic siliceous materials or acidic zeolites; inorganic carriers, such as oxides, coated with inorganic acids, mono, di, tri or polyacids; oxides or mixed oxides or heteropolyacids.
  • the catalyst may consist of an acid phase selected from acidic resins such as Amberlyst resins (in particular Amberlyst 15 and 36), zeolites, Nafion ⁇ composites (based on fluorinated polymers of sulphonic acid), and chlorinated aluminas. , acids and salts of phosphotungstic and / or silicotungstic acids, and various solids of the metal oxide type such as tantalum oxide Ta 2 O 5 , niobium oxide Nb 2 O 5 , alumina
  • R 1 and R 2 which are identical or different, are either the hydrogen atom H, a linear or branched alkyl radical, saturated or unsaturated, optionally containing a second ketonic or ether type function, or a cyclic or aromatic radical; , from 1 to 22 carbon atoms.
  • R3 is either the hydrogen atom H, or a linear or branched alkyl radical, saturated or unsaturated, cyclic or aromatic, of 1 to 22 carbon atoms, Ri and R 2 as defined above.
  • R 4 and R 5 represent either the hydrogen atom H, or linear or branched alkyl radicals, saturated or unsaturated, or cyclic or aromatic radicals, of 1 to 22 carbon atoms.
  • R ⁇ is a linear or branched alkylene group, saturated or unsaturated, cyclic or aromatic, of from 0 to 22 carbon atoms, Ri and R 2 as defined above.
  • R 1 and / or R 2 are alkyl or alkenyl radicals
  • the total number of carbon atoms in R 1 + R 2 is greater than or equal to 4 and preferably greater than 6.
  • R 1 and / or R 2 includes a second function of the carbonyl (aldehyde or ketone) type, cyclic di and / or triacetals can be obtained.
  • R 1, R 2, R 3 and R 4 are linear or branched alkyl groups, saturated or unsaturated, cyclic or aromatic, of 1 to 22 carbon atoms and R 5 is either CH 2 , CHOH, or a linear or branched alkylene group saturated or unsaturated, cyclic or aromatic, from 0 to 22 carbon atoms.
  • the acetalization reaction may be carried out at a temperature in the region of room temperature, which will generally be between 5 and 200 ° C., and at a pressure generally of between 100 kPa and 8000 kPa.
  • the reaction medium must be strongly stirred to promote contacting of the organic fraction containing the aldehyde / ketone not soluble in water with the aqueous fraction containing glycerol.
  • the synthesis of the cyclic acetals by extraction of the polyol in solution is carried out in several consecutive reaction stages (extractions with respect to the polyol).
  • the first stage a portion of the polyol of the concentrated solution is extracted using a low concentration of aldehyde / ketone.
  • the polyol solution is thus further diluted and the polyol is reacted with a higher concentration of aldehyde / ketone, this operation being repeated as much as necessary with progressive increase of the relative concentration of aldehyde / ketone.
  • the reaction time in each extractive stage depends on the kinetics of reaction and therefore the concentration in each of the reagents.
  • the temperature and pressure can be adjusted independently in each reaction stage. A higher temperature makes it possible to accelerate the reactions, but also shifts the equilibrium. Therefore, it is preferable to use higher concentrations of aldehyde / ketone in successive stages.
  • the first reaction stage operates at a higher temperature, and / or with a shorter reaction time than the later stages.
  • a reaction stage comprises a reagent mixing zone, a reaction zone and a separation zone of the aqueous phase and the organic phase. In certain reactor configurations, some of these zones can be confused.
  • the process of the invention is particularly suitable for the treatment of aqueous solutions comprising impurities in solution.
  • the quality of glycerol called Glycerin Brute contains glycerol in aqueous solution, but also sodium or potassium salts, in the form of sodium or potassium chloride, or sodium or potassium sulfate, salts that have origin the transesterification catalyst of vegetable oils or animal fats having for example allowed the formation of biodiesel.
  • the process of the present invention allows the direct treatment of the Glycerin Brute at glycerol concentrations greater than 20% by weight.
  • the aqueous effluents of the reaction can be returned to the neutralization stage of the effluents of the unit of biodiesel or transesterification.
  • the products resulting from the reaction are in a mixture.
  • the cyclic acetal is then separated from the organic phase by any separation technique well known to those skilled in the art.
  • the aqueous phase can be easily recycled.
  • the reactive separation process solves many of the difficulties of the prior art. It allows in particular to have a continuous process, while often the synthesis of acetals is carried out batch processes.
  • Another advantage of the process consists in that the reagent mixture is not necessarily necessarily water-free since it is continuously separated during the process. In discontinuous reactors, water being a product of the reaction, an additional presence of water displaces the equilibria towards the formation of reagents, which leads to a fall in yields.
  • anhydrous reagents In the process of the invention, a reagent mixture containing from 0 to 80% by weight water, preferably from 0 to 60% water and more preferably from 1 to 50% may be used.
  • the cyclic acetals may undergo subsequent transformations depending on the purpose of their use. They may for example be converted by transacetalization into another cyclic acetal adapted to the application. They may be subjected to hydrolysis if the desired product is pure glycerol, the aldehyde or ketone resulting can be reused in the process.
  • cyclic glycerol acetals such as the preparation of crosslinking agents, solvents, synthetic intermediates and fuel additives, and can be found in many fields such as pharmaceuticals and cosmetics, bioregulators in agrochemistry, biodegradable polymers (especially in the formulation of chewing gum), the preparation of glycerides.
  • the by-products of the reaction may be ethers obtained by dehydration of the alcohol
  • polyacetals obtained by subsequent reaction of the aldehyde / ketone on the acetal.
  • the formation of ethers occurs in general when increasing the reaction temperature in order to shift the equilibrium.
  • the displacement of equilibria being ensured by the elimination of one of the products of the reaction, and not by an increase in temperature, the appearance of such by-products is thus reduced.
  • the process according to the invention thus makes it possible to obtain not only high conversions, but also high selectivities.
  • Example 1 This example illustrates the reactive extraction of glycerol by acetalization with heptanaldehyde, using hydrochloric acid as a catalyst, and with a heptanaldehyde / glycerol molar ratio of 1.
  • An aqueous solution of glycerol (60% by weight of glycerol, 40% by weight of water) containing 10 mmol of glycerol (ie 0.920 g) is mixed with 10 mmol of heptanaldehyde (ie 1.14 g) to have a molar ratio.
  • heptanal / glycerol 1.
  • a solution of 35% hydrochloric acid is added to the aqueous solution of glycerol + heptanaldehyde in a proportion of 15% relative to glycerol.
  • the mixture is then heated at 40 ° C. for 5 hours with stirring. Then the two phases are separated by decantation, and the organic phase is washed with water until a neutral pH.
  • the solution obtained is then dried over anhydrous MgSO 4 and then concentrated by evaporation in vacuo.
  • the product obtained was analyzed by NMR and mass spectrometry, and quantified by chromatographic analysis. The yield of glycerol acetal obtained is 43% by weight relative to heptanaldehyde.
  • Example 2 The cyclic acetal of glycerol and heptanaldehyde is obtained as in the preceding example, but using a heptanaldehyde / glycerol molar ratio of 0.6, and with a glycerol mass of 1.47 g (16 mmol) instead of 0.920 g. In this case, the yield of the synthesis is 73% by weight relative to heptanaldehyde.
  • the cyclic acetal of glycerol and heptanaldehyde is obtained as in Example 1, but using a heptanaldehyde / glycerol molar ratio of 0.33, and with a glycerol mass of 2.76 g (30 mmol) instead 0.920 g. In this case, the yield of the synthesis is 79% by weight.
  • the catalyst is then filtered. Then the two liquid phases are separated by decantation. The aqueous phase is extracted several times with dichloromethane. The dichloromethane solution is then added to the organic phase, which is then concentrated by evaporation under vacuum. The product obtained was analyzed by NMR and mass spectrometry, and quantified by chromatographic analysis. The yield of glycerol acetal obtained is 80% by weight relative to heptanaldehyde.
  • Example 5 is carried out as Example 4, but using a more dilute aqueous solution of glycerol (40% by weight of glycerol instead of 60% by weight). The yield of acetal is then 71% by weight relative to heptanaldehyde.
  • a Beta zeolite with a Si / Al atomic ratio of 13 is added to the aqueous solution of glycerol + heptanaldehyde in a proportion of 20% relative to glycerol. The mixture is then heated at 40 ° C. for 5 hours with stirring.
  • the catalyst is then filtered. Then, the two liquid phases are separated by decantation, and the aqueous phase is extracted several times with dichloromethane. The dichloromethane solution is then added to the organic phase, which is then concentrated by evaporation under vacuum. The product obtained was analyzed by NMR and mass spectrometry, and quantified by chromatographic analysis. The yield of glycerol acetal obtained is 42% by weight relative to heptanaldehyde.
  • composition of the organic phase is given in percentages determined from the chromatogram and is presented in Table 1, Figure 1 and 2.
  • Table 1 Composition of the organic phase
  • the glycerol content of the aqueous phase was determined from the ratio of glycerol / decanol areas obtained at time 0 and taken as a reference (100%). Thus, the same ratio calculated at 15, 30 min, 1, 2, 4, 6 and 24 h is expressed as a percentage with respect to the initial ratio.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP07858522A 2006-10-09 2007-10-08 Verfahren für die synthese zyklischer acetale mittels reaktiver extraktion eines polyols in einer konzentrierten lösung Withdrawn EP2076505A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0654153A FR2906807A1 (fr) 2006-10-09 2006-10-09 Procede de synthese d'acetals cycliques par extraction reactive d'un polyol en solution concentree
PCT/FR2007/052091 WO2008043947A1 (fr) 2006-10-09 2007-10-08 Procédé de synthèse d'acétals cycliques par extraction réactive d'un polyol en solution concentrée

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EP2076505A1 true EP2076505A1 (de) 2009-07-08

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US (1) US20100099894A1 (de)
EP (1) EP2076505A1 (de)
FR (1) FR2906807A1 (de)
WO (1) WO2008043947A1 (de)

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FR2931150B1 (fr) * 2008-05-19 2010-07-30 Rhodia Poliamida E Especialidades Ltda Procede de purification du glycerol brut
BRPI0902550B1 (pt) * 2009-01-05 2018-04-24 Senai/dr-ba-serviço Nacional De Aprendizagem Industrial, Departamento Regional Da Bahia Processo de purificação da glicerina loura, oriunda da transesterificação do biodiesel
DE102009027420A1 (de) 2009-07-02 2011-01-05 Evonik Degussa Gmbh Verfahren zur Herstellung von Acrolein
FR2950894B1 (fr) * 2009-10-06 2011-12-23 Arkema France Utilisation d'acetals de glycerol comme agents de coalescence pour laques, peintures ou vernis et compositions les comprenant
FR2964658B1 (fr) * 2010-09-15 2013-01-04 Rhodia Operations Procede de fabrication de dioxolane
US9056313B2 (en) 2011-06-24 2015-06-16 Eastman Chemical Company Catalysts for the production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals
US9388105B2 (en) 2011-06-24 2016-07-12 Eastman Chemical Company Production of hydroxy ether hydrocarbons by liquid phase hydrogenolysis of cyclic acetals or cyclic ketals
US9000229B2 (en) 2011-06-24 2015-04-07 Eastman Chemical Company Production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals
US8969598B2 (en) 2011-06-24 2015-03-03 Eastman Chemical Company Production of cyclic acetals or ketals using liquid-phase acid catalysts
US8829207B2 (en) * 2011-06-24 2014-09-09 Eastman Chemical Company Production of cyclic acetals by reactive distillation
US8829206B2 (en) 2011-06-24 2014-09-09 Eastman Chemical Company Production of cyclic acetals or ketals using solid acid catalysts
US8785697B2 (en) 2011-06-24 2014-07-22 Eastman Chemical Company Nickel modified catalyst for the production of hydroxy ether hydrocarbons by vapor phase hydrogenolysis of cyclic acetals and ketals
US10285972B2 (en) 2014-01-23 2019-05-14 Greenyn Biotechnology Co., Ltd Trans-2-nonadecyl-4-hydroxymethyl-1,3-dioxolane and producing methodthereof
TWI553000B (zh) * 2014-01-23 2016-10-11 綠茵生技股份有限公司 反式－２－１９烷基－４－羥甲基－１，３－二氧戊環化合物及其製備方法

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WO2008043947A1 (fr) 2008-04-17
FR2906807A1 (fr) 2008-04-11

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