EP2828230A1 - Procédé de préparation d'éther de glycérol et d'éther de glycol - Google Patents

Procédé de préparation d'éther de glycérol et d'éther de glycol

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Publication number
EP2828230A1
EP2828230A1 EP13714588.4A EP13714588A EP2828230A1 EP 2828230 A1 EP2828230 A1 EP 2828230A1 EP 13714588 A EP13714588 A EP 13714588A EP 2828230 A1 EP2828230 A1 EP 2828230A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
formula
mequi
acid
compound
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Withdrawn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
EP13714588.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Gérard Mignani
Marc Lemaire
Eric Da Silva
Wissam Dayoub
Yann Raoul
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.)
Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
FONDS DE DEVELOPPEMENT DES FILIERES DES OLEAGINEUX ET PROTEAGINEUX FIDOP
Universite Claude Bernard Lyon 1
Original Assignee
Centre National de la Recherche Scientifique CNRS
Rhodia Operations SAS
FONDS DE DEVELOPPEMENT DES FILIERES DES OLEAGINEUX ET PROTEAGINEUX FIDOP
Universite Claude Bernard Lyon 1
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 Centre National de la Recherche Scientifique CNRS, Rhodia Operations SAS, FONDS DE DEVELOPPEMENT DES FILIERES DES OLEAGINEUX ET PROTEAGINEUX FIDOP, Universite Claude Bernard Lyon 1 filed Critical Centre National de la Recherche Scientifique CNRS
Publication of EP2828230A1 publication Critical patent/EP2828230A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • C07C43/13—Saturated ethers containing hydroxy or O-metal groups
    • 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
    • C07D317/32—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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C07D317/36—Alkylene carbonates; Substituted alkylene carbonates

Definitions

  • the present invention relates to a process for the preparation of glycerol ether and glycol ether.
  • Glycerol and its derivatives are important by-products of the industry, including the biodiesel industry. It is therefore particularly interesting to find new ways of valuing these products.
  • Glycerol ethers and glycol ethers can be used in many fields such as cosmetics, detergents, washing formulations and in the pharmaceutical field. These ethers can constitute a new range of surfactants particularly interesting since derived from biosourced materials. However, few synthetic processes make it possible to obtain these ethers in a simple way and at a lower cost.
  • JP200-1 19205 is known, in particular, from a process for the preparation of glycerol ether from glycerol carbonate by reaction in the presence of a base (especially KOH).
  • a base especially KOH
  • the implementation of this method does not make it possible to obtain good yields of glycerol ether, in fact, the transcarbonation compound is formed mainly.
  • the object of the present invention is to provide a process for the selective preparation of glycerol ether or derivatives of glycerol and glycol ether.
  • Another object of the present invention is also to provide such a process which makes it possible to obtain, with good yields, the desired ether.
  • Another object of the present invention is also to provide a process for the preparation of surfactants from biosourced compounds.
  • Yet another object is to provide a continuous process for preparing glycerol ether or glycerol derivatives and glycol ether.
  • the present invention relates to a process for the preparation of glycerol ether or glycol ether of formula (I) and / or ( ⁇ ) comprising the reaction of a compound of formula (II) with a compound of formula (III) in the presence of a heterogeneous acidic catalyst
  • R 1 is a hydrogen atom or a linear or branched alkyl radical comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms;
  • R 2 is a hydrogen atom; a linear or branched alkyl radical comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms; or a group of the formula - (CH 2 ) n OH, wherein n is an integer from 0 to 5, and preferably n is 0 or 1;
  • R 3 is a linear or branched alkyl radical which may comprise one or more unsaturations, comprising from 1 to 40 carbon atoms, and which may optionally comprise 1 or more hydroxyl (OH) substituents.
  • R 1 is a hydrogen atom
  • R 2 is -CH 2 OH
  • the compound (II) thus preferred is glycerol carbonate
  • the compound formed is a compound of formula ( I):
  • R 3 is a linear or branched alkyl radical which may comprise one or more unsaturations, comprising from 1 to 40 carbon atoms.
  • R 3 is a linear or branched alkyl radical which may comprise one or more unsaturations, comprising from 12 to 40 carbon atoms, preferably from 24 to 30 carbon atoms.
  • R 3 is a linear or branched alkyl radical which may comprise one or more unsaturations, comprising from 1 to 15 carbon atoms.
  • the process relates to the preparation of glycerol ether.
  • the process relates to the preparation of glycol ether.
  • the heterogeneous acid catalyst of the invention has an acid site concentration greater than or equal to 0.01 mequi / g (or mEq / g or m / g) (milli equivalent of H + ions per gram) of catalyst, preferably from 0.01 to 10 mequi / g (or mEq / g or m / g), more preferably from 0.01 to 6 mequi / g (or mEq / g or m / g), preferably from 0 to , 01 to 5 mequi / g (or meq / g or m / g).
  • the term "acid site concentration” means the surface acidity due to H + protons at the surface of the catalyst. This acidic site concentration is determined by any method known to those skilled in the art and in particular in the usual manner by determining the number of milliequivalents of H + protons reduced to 1 g of catalyst (mequi / g (Meq / g or m / g). ) of catalyst). The acidic site concentration in mEq / g corresponds to the ion exchange capacity of the catalyst expressed in mEq of H + per gram of catalyst.
  • the heterogeneous catalyst according to the invention has a specific surface area measured by the BET method of from 5 to 500 m 2 / g, preferably from 10 to 100 m 2 / g.
  • the specific surface is determined by the BET method, for example by the method of adsorption and nitrogen desorption.
  • the heterogeneous catalyst according to the invention is characterized by a Hammett (Ho) constant of from -3 to -12, preferably from -5 to -12.
  • Ho Hammett
  • the Hammett constant can be determined by any method known to those skilled in the art and is in particular determined by a standard colorimetric method known as the Tanabe method (TANABE et al., The Journal of Physical Chemistry, (1976) 15, 1723).
  • the acidic catalyst AH is reacted with a color indicator B, the reaction leads to the formation of A " and BH +, the value Ho is then determined by the formula (A):
  • the catalyst is selected from the group consisting of acidic forms of ion exchange resins; carriers impregnated with sulfuric acid, hydrochloric acid, niobic acid, hydrofluoric acid, antimony pentafluoride, heteropolyacids, triflic acid, or sulfonic or phosphoric acid; sulphated zirconia; zeolites, in particular zeolite alumino-silicate, for example zeolite Y characterized by a faujasite structure; and mixed oxides, including Ti0 2 / Al 2 0 3, Re0 7 / Al 2 0 3, Ti0 2 / Zr0 2, Si0 2 / AI 2 03.
  • the supports are in particular chosen from metal oxides, in particular Al 2 O 3 , ZrO 2 , TiO 2 ; Si0 2 ; or coals.
  • the catalyst is chosen from the acidic forms of the ion exchange resins; substrates impregnated with sulfuric acid or sulphonic acid; and sulphated zirconias.
  • the heterogeneous catalyst is chosen from the acidic forms of the ion exchange resins.
  • the acidic ion exchange resins may in particular be chosen from acidic exchange resins carrying sulfonic groups. They may in particular be chosen from resins consisting of a polystyrenic skeleton bearing sulphonic groups or from perfluorinated resins bearing sulphonic groups.
  • the resins consisting of a polystyrene backbone are styrene-divinylbenzene copolymers containing sulfonic groups.
  • a resin is obtained by polymerization of styrene and divinylbenzene under the influence of an activation catalyst, most often in suspension. Beads or granules are obtained which are then treated with concentrated sulfuric or sulfochloric acid. The proportion of sulfonic groups with respect to the polymer mass may be variable and will be taken into account when determining the amount of polymer to be used.
  • Such resins are in particular commercially available under the name Amberlyst® (marketed by Dow).
  • Amberlyst® marketed by Dow.
  • these resins are chosen from Amberlyst® 35, Amberlyst® 36, Amberlyst® 70 or Amberlyst® 21.
  • the perfluorinated resins containing sulphonic groups are copolymers of tetrafluoroethylene and of perfluoro [2- (fluorosulfonyl-ethoxy) propyl] vinyl ether, in particular those sold under the name Nafion®.
  • These resins correspond to the following formula:
  • n is an integer of 5 to 13 and x is generally about 1000.
  • the resins are resins consisting of a polystyrenic skeleton bearing sulphonic groups.
  • the catalyst is used in proportions of 2% to 40%, preferably 5% to 20% by weight relative to the weight of compound of formula (II).
  • the molar ratio compound of formula (II) / compound of formula (III) is from 1/1 to 1/5, preferably from 1/2 to 1/4.
  • the process of the invention may be carried out at a temperature of 100 ° C to 200 ° C, preferably 100 ° C to 170 ° C, for example 100 ° C to 150 ° C.
  • the duration of the process of the present invention may be from 30 minutes to 24 hours, preferably from 30 minutes to 12 hours.
  • the process of the invention may be carried out batchwise or continuously, it is preferably carried out continuously.
  • the process of the invention advantageously makes it possible to obtain glycerol ethers of purity greater than or equal to 90%, preferably greater than or equal to 99%.
  • the compound of formula (III) when the compound of formula (III) is a fatty alcohol, that is to say when R 3 is a linear or branched alkyl comprising from 12 to 40 carbon atoms, preferably from 24 to 30 carbon atoms, the ethers thus obtained may in particular be used as surfactants. These ethers may advantageously be used as surfactants in detergent compositions, in cosmetic compositions, in washing formulations and in the pharmaceutical field.
  • the process may comprise a preliminary step of preparing the compound of formula (II). This preliminary step is performed by reaction between a compound of formula (IV) and carbon dioxide, in the presence of a lanthanide catalyst:
  • R 1 and R 2 are as defined for formula (I).
  • the lanthanide catalyst is selected from the family of lanthanides, and more particularly from the rare earth group, supported or unsupported.
  • rare earths defined in the rest of the description by the generic term Ln
  • Ln means the chemical elements chosen from the group consisting of cerium (Ce), lanthanum (La), praseodymium (Pr), neodymium ( Nd), yttrium (Y), gadolinium (Gd), samarium (Sm) and holmium (Ho), alone or as a mixture, preferably cerium, lanthanum, praseodymium and neodymium, alone or in mixture.
  • Ce cerium
  • La lanthanum
  • Pr praseodymium
  • Nd neodymium
  • Y yttrium
  • Gd gadolinium
  • Sm samarium
  • Ho holmium
  • the catalyst is selected from the group consisting of lanthanide oxides of formula Ln 2 0 3 (for lanthanum, neodymium, yttrium, gadolinium, samarium and holmium) or Ce0 2 or Pr 6 O, lanthanide carbonates of formula Ln 2 (CO 3 ) 3 , lanthanide hydroxycarbonates of formula Ln (OH) (CO 3 ), lanthanide oxycarbonates of formula Ln 2 (CO 3 ) 2 and the hydroxides of lanthanides of formula Ln (OH) 3 , alone or as a mixture.
  • lanthanide oxides of formula Ln 2 0 3 for lanthanum, neodymium, yttrium, gadolinium, samarium and holmium
  • Ce0 2 or Pr 6 O Ce0 2 or Pr 6 O
  • lanthanide carbonates of formula Ln 2 (CO 3 ) 3 lanthanide hydroxycarbonates of formula Ln (OH)
  • the catalyst is selected from the group consisting of lanthanide oxides, lanthanide carbonates and lanthanide hydroxycarbonates, alone or in admixture; preferably the catalyst is selected from the group consisting of lanthanide oxides, lanthanide carbonates, alone or in admixture.
  • the catalyst is a rare earth oxide.
  • the catalyst of the prior step is selected from the group consisting of Ce0 2 and Pr 6 On.
  • the catalyst of the preceding step is in oxide form and has a specific surface area of at least 5 m 2 / g, preferably at least 10 m 2 / g, more preferably at least 30 m 2 / g.
  • the catalyst of the prior stage is doped with Lewis acid type metals, for example transition metals, alkaline earth metals and metalloids.
  • these metals are selected from the group consisting of iron (Fe (II) and Fe (III)), copper (Cu (I) and Cu (III)), aluminum (Al (III) )), titanium (Ti (IV)), boron (B (III)), zinc (Zn (II)) and magnesium (Mg (II)).
  • these metals are selected from the group consisting of iron (Fe (II) and Fe (III)), copper (Cu (I) and Cu (III)), titanium (Ti (IV)) and zinc (Zn (ll)).
  • the catalyst is a rare earth oxide modified with transition metals.
  • the relative percentage of metals with respect to the lanthanide material is between 1 and 10% by weight, preferably between 1 and 5% by weight.
  • the catalyst in order to minimize costs, may be a mixed system based on rare earths and other minerals such as ZnO, MgO, Al 2 O 3 or SiO 2 .
  • This particular embodiment makes it possible to provide additional properties in terms of both the acid-base properties and the mechanical properties of the catalysts.
  • the molar ratio between the compound of formula (IV) and CO 2 is between 1 and 150 equivalents in moles, preferably between 1 and 100 equivalents.
  • the preliminary step of preparation of the compound of formula (II) is carried out at autogenous pressure or at atmospheric pressure. According to the invention, the preliminary step of preparing the compound of formula (II) is carried out at a temperature of between 25 and 250 ° C., preferably between 25 and 200 ° C., for example between 50 and 150 ° C. .
  • the amount of catalyst is between 0.01 and 50% by weight relative to the weight of compound of formula (IV), preferably between 1 and 25% by weight, preferably between 3 and 15% by weight.
  • the aqueous phase is extracted with 2 ⁇ 25 mL of CH 2 Cl 2 .
  • the organic phases are combined and the CH 2 Cl 2 is evaporated under reduced pressure.
  • the crude reaction product is finally purified by chromatography on a flash silica column (eluent (AcOEt / cyclohexane: 1/4 to 1/1)) to give 1-O-octylether of glycerol with an isolated yield of 45%.
  • the aqueous phase is extracted with 2 ⁇ 25 mL of CH 2 Cl 2 .
  • the organic phases are combined and the CH 2 Cl 2 is evaporated under reduced pressure.
  • the reaction crude analyzed without purification by gas chromatography.
  • the octyl ether of glycerol is detected with a GC yield of 15%.
  • the aqueous phase is extracted with 2 ⁇ 10 mL of CH 2 Cl 2 .
  • the organic phases are combined and the CH 2 Cl 2 is evaporated under reduced pressure.
  • the crude reaction product is finally purified by chromatography on a flash silica column (Eluent (AcOEt / cyclohexane: 1/4 to 1/1)) to give glycerol 1-O-pentyl ether in an isolated yield of 49%.
  • the aqueous phase is extracted with 2 ⁇ 25 mL of CH 2 Cl 2 .
  • the organic phases are combined and the CH 2 Cl 2 is evaporated under reduced pressure.
  • the crude reaction product is finally purified by chromatography on a flash silica column (eluent (AcOEt / cyclohexane: 1/4 to 1/1)) to give 1-O-tetradecylether of glycerol with an isolated yield of 45%.
  • the aqueous phase is extracted with 2 ⁇ 10 mL of CH 2 Cl 2 .
  • the organic phases are combined and the CH 2 Cl 2 is evaporated under reduced pressure.
  • the crude reaction product is finally purified by chromatography on a flash silica column (eluent (AcOEt / cyclohexane: 0/1 to 1/10)) to give the 1-O-pentyl ether of ethylene glycol with an isolated yield of 46%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP13714588.4A 2012-03-23 2013-03-25 Procédé de préparation d'éther de glycérol et d'éther de glycol Withdrawn EP2828230A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1252624A FR2988391B1 (fr) 2012-03-23 2012-03-23 Procede de preparation d'ether de glycerol
PCT/EP2013/056280 WO2013139995A1 (fr) 2012-03-23 2013-03-25 Procédé de préparation d'éther de glycérol et d'éther de glycol

Publications (1)

Publication Number Publication Date
EP2828230A1 true EP2828230A1 (fr) 2015-01-28

Family

ID=48049971

Family Applications (1)

Application Number Title Priority Date Filing Date
EP13714588.4A Withdrawn EP2828230A1 (fr) 2012-03-23 2013-03-25 Procédé de préparation d'éther de glycérol et d'éther de glycol

Country Status (7)

Country Link
US (1) US20150080613A1 (https=)
EP (1) EP2828230A1 (https=)
CN (1) CN104302607A (https=)
BR (1) BR112014023486A2 (https=)
FR (1) FR2988391B1 (https=)
IN (1) IN2014DN08460A (https=)
WO (1) WO2013139995A1 (https=)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2026005835A1 (en) 2024-06-24 2026-01-02 Dow Global Technologies Llc Low-voc coalescent for coatings

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2448767A (en) * 1942-12-05 1948-09-07 Mellon Inst Of Ind Res Process of hydroxyethylation
US5104987A (en) * 1990-09-20 1992-04-14 Union Carbide Chemicals & Plastics Technology Corporation Alkoxylation of active hydrogen-containing compounds
JP2000119205A (ja) * 1998-10-09 2000-04-25 Sakamoto Yakuhin Kogyo Co Ltd グリセリルエーテル化合物の製造法
FR2950881B1 (fr) * 2009-10-05 2012-02-17 Rhodia Operations (poly)glycerols, leurs procedes de fabrication et leurs utilisations

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2013139995A1 *

Also Published As

Publication number Publication date
FR2988391B1 (fr) 2014-08-22
US20150080613A1 (en) 2015-03-19
CN104302607A (zh) 2015-01-21
BR112014023486A2 (pt) 2017-08-22
FR2988391A1 (fr) 2013-09-27
WO2013139995A1 (fr) 2013-09-26
IN2014DN08460A (https=) 2015-05-08

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