EP4377281A1 - Oxidationsstabile dianhydrohexitolzusammensetzung mit gallinsäureester - Google Patents

Oxidationsstabile dianhydrohexitolzusammensetzung mit gallinsäureester

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Publication number
EP4377281A1
EP4377281A1 EP22750997.3A EP22750997A EP4377281A1 EP 4377281 A1 EP4377281 A1 EP 4377281A1 EP 22750997 A EP22750997 A EP 22750997A EP 4377281 A1 EP4377281 A1 EP 4377281A1
Authority
EP
European Patent Office
Prior art keywords
product
dry weight
isosorbide
gallic acid
composition
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
EP22750997.3A
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English (en)
French (fr)
Inventor
René SAINT-LOUP
Théodore VANBESIEN
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.)
Roquette Freres SA
Original Assignee
Roquette Freres SA
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 Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP4377281A1 publication Critical patent/EP4377281A1/de
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C07B63/04—Use of additives

Definitions

  • the present invention relates to a method for improving the oxidative stability of compositions of an internal dehydration product of a hydrogenated sugar, in particular an isosorbide composition, said method being based on the setting work of gallic acid esters. It also relates to the compositions thus obtained and to their various uses.
  • hexitols C6 hydrogenated sugars
  • sorbitol C6 hydrogenated sugars
  • mannitol C6 hydrogenated sugars
  • iditols C6 hydrogenated sugars
  • dianhydrohexitols encompasses isosorbide (1,4-3,6-dianhydro-sorbitol), isomannide (1,4-3,6 dianhydro-mannitol), isoidide (1, 4 - 3,6- dianhydro-iditol) of the following formulas, as well as mixtures of these products:
  • alkyl or alkenyl derivatives which can be used as plasticizers for polymers, adhesives or inks; - specific biphosphites which can be used as polymer stabilizers or lubricants;
  • polyols such as hexitols
  • a dehydration step for example sorbitol
  • desired dehydration product for example isosorbide
  • isosorbide isomers such as isomannide and isoidide
  • these derivatives possibly including, for example when the desired product is isosorbide, co-products of the deoxy monoanhydro hexitols, monoanhydro pentitols, monoanhydro tetritols type, anhydro hexoses, hydroxymethyl furfural, or glycerine:
  • patent GB 613 444 which describes the production, by dehydration in a water/xylene medium, of an isosorbide composition then subjected to a distillation and then recrystallization treatment in an alcohol/ether mixture.
  • dehydration catalysts hereinafter a gaseous hydrogen halide and liquid hydrogen fluoride
  • carboxylic acids as co-catalysts
  • This invention is the subject of patent EP 1 446 373, protecting a process for the preparation of a product composition of internal dehydration of a hydrogenated sugar, characterized in that it comprises: a) a step distillation of a medium containing said product of internal dehydration in order to obtain a distillate enriched in this product, b) optionally, at least one subsequent stage of purification of the distillate thus obtained, c) a subsequent stage of bringing the distillate obtained during step a), then optionally subjected to step b), with an agent capable of improving the stability of the product of internal dehydration mainly contained in the distillate, the said agent not being in gaseous form, d) optionally, a subsequent step of shaping the resulting composition of internal dehydration product of a hydrogenated sugar.
  • step c This document relates a certain number of possibilities for the improvement agent implemented during step c), and which can be chosen from:
  • boron or aluminum such as sodium borohydride (NaBH4) or lithium aluminum hydride (UAIH4);
  • antioxidants and in particular nitrogen-based compounds, in particular amines, aromatic or not, additionally containing or not containing at least one alcohol function, such as hydroxylamine, morpholine, and their derivatives;
  • - antioxidant compounds based on phosphorus or sulfur such as phosphites, phosphonites, sulphites, salts of thiodipropionic acid esters and mixtures thereof;
  • metal deactivating agents such as complexing or chelating agents for metals of natural origin
  • vitamin C ascorbic acid
  • erythorbic acid lactic acid
  • citric acid citric acid
  • gallic acid tocopherols
  • derivatives (in particular salts) of all of these products BHT, butylhydroxyanisole (BHA) and any mixtures of these products.
  • stable composition within the meaning of document EP 1 446373, is meant a composition which, stored in a non-inert atmosphere for a period of at least one month and at a temperature of 40° C., has both a formic acid content less than 0.0005% and an overall monoanhydrohexose content of less than 0.005%, these percentages being expressed by dry weight relative to the dry weight of said composition.
  • This stability is, for the compositions obtained by means of the aforementioned process, greater than 1 month and can reach at least 2 months, preferably at least 6 months and even more preferably at least one year.
  • document EP 1 446 373 exemplifies sodium borohydride, morpholine, BHT, vitamin C, sodium borate, sodium hydroxide, and disodium phosphate, the best results (stability of 6 months) being obtained for sodium borohydride and morpholine.
  • the induction period is the period at the start of the oxidation process during which the reactions are slow, due to a low concentration of reaction intermediates. Once this period has elapsed, the reactions are faster, which results in a sudden change in the oxygen pressure.
  • the induction time is thus determined, which corresponds to the duration of this initial induction period.
  • this method has made it possible to demonstrate that certain compounds of the prior art, pondered to be effective with respect to stability at pH, had no effect on the oxidation phenomenon: this is the case of disodium phosphate. It also made it possible to demonstrate the interest of DEA and TEA, as agents improving resistance to oxidation. But it has above all proved to be particularly discriminating, in particular by ruling out antioxidant agents known elsewhere but having a surprisingly negative effect on isosorbide, and by releasing a class of compounds that are particularly effective in terms of antioxidant power on the isosorbide: esters of gallic acid. No compound known until then had made it possible to achieve such an antioxidant power on isosorbide, not even DEA and TEA.
  • a first object of the present invention consists of a method for preparing a composition of internal dehydration product of a hydrogenated sugar, comprising: a) a step of distilling a medium containing said dehydration product in order to obtain a distillate enriched in this product, b) optionally, at least one subsequent stage of purification of the distillate thus obtained, c) a subsequent stage of bringing together the distillate obtained during stage a), then optionally subjected to step b), with at least one gallic acid ester, d) optionally, a subsequent step of shaping the resulting composition of internal dehydration product of a hydrogenated sugar.
  • the gallic acid ester used in step c) is chosen from alkyl esters, more preferably from ethyl gallate and propyl gallate and mixtures thereof. . Even more preferably, the gallic acid ester used in step c) is propyl gallate.
  • step c) also uses a phosphate compound, preferably disodium phosphate.
  • step c) also uses an amine, preferably chosen from alkylamines, more preferably from diethanolamine and triethanolamine, and which is very preferably diethanolamine.
  • the method according to the invention is advantageously characterized in that the gallic acid ester used in step c) is used at a rate of 0.0001 to 2%, preferably from 0.001 to 2 %, more preferably from 0.002 to 1.5%, even more preferably from 0.002 to 0.1%, these percentages being expressed in dry weight of gallic acid ester relative to the dry weight of the product of internal dehydration of hydrogenated sugar then mainly present in the distillate, for example isosorbide then present in this medium.
  • the phosphate compound used in step c) is advantageously used at a rate of 0.0001 to 2%, preferably 0.001 to 2%, more preferably 0.002 to 1.5%, even more preferably from 0.002 to 0.1%, these percentages being expressed as dry weight of said phosphate compound relative to the dry weight of the product of internal dehydration of hydrogenated sugar then predominantly present in the distillate, for example isosorbide then present in this medium.
  • the amine implemented in step c) is advantageously used at a rate of 0.0001 to 2%, preferably 0.001 to 2%, more preferably 0.002 to 1.5%, even more preferably from 0.002 to 0.1%, these percentages being expressed by dry weight of said amine relative to the dry weight of the product of internal dehydration of hydrogenated sugar then mainly present in the distillate, for example of the isosorbide then present in this medium.
  • the medium subjected to step a) of distillation can be of very varied nature, including in terms of dry matter, temperature and / or of purity into the desired dehydration product.
  • the purity of the medium subjected to step a) of the desired product for example isosorbide
  • an isosorbide composition consisting of the medium resulting directly from the dehydration reaction proper and having for example a purity of the desired product, for example of isosorbide, of the order from 50 to 80%.
  • said composition already results from one or more previous purification operations, in particular by distillation and/or crystallization and has for example a purity of desired product, for example of isosorbide, greater than 80%.
  • step a) of distillation is followed by a step b) of purification of the resulting distillate.
  • step b) consists of a purification step according to which the distillate, generally placed in solution, is treated with at least one purification means chosen from among decolorization means and ion exchange means.
  • discoloration means in particular activated carbon in granular or pulverulent form and adsorption resins.
  • granular activated carbon such as the CECA DC 50 product
  • pulverulent activated carbon such as the NORIT SX+ product
  • a resin such as those called DUOLITE XAD 761, MACRONET MN- 600 or MACRONET MN-400.
  • ionic exchange one understands in particular the anionic resins, weak or strong, and the cationic resins, weak or strong.
  • a strong anionic resin such as AMBERLITE IRA 910 resin or a strong cationic resin such as PUROLITE C 150 S resin.
  • the ion exchange means can advantageously comprise at least one anionic resin and at least one cationic resin.
  • this means is composed of a mixed bed of anionic resin(s) and cationic(s) or of a succession of cationic(s) then anionic(s) resins or of a succession of anionic(s) then cationic resin(s).
  • the distillate obtained during step a) is treated in any order with at least one activated carbon and with at least one resin. , ionic or non-ionic.
  • said distillate is treated first with an activated carbon then with at least one resin and then again with an activated carbon.
  • the Applicant Company has found that it is particularly advantageous for the composition subjected to purification step b) to already have certain characteristics in terms of maximum content of particular impurities, for example formic acid and monoanhydrohexose species. It also found that such a content could in particular be guaranteed by directly subjecting the distillate obtained during step a) to said purification step b).
  • the process according to the invention can therefore be characterized in that the distillate subjected to said step b) has a formic acid content of less than 0.002% and a monoanhydrohexose content of less than 0.02%, these percentages being expressed in dry weight relative to the dry weight of the product of internal dehydration of hydrogenated sugar then predominantly present in said distillate, for example to the dry weight of isosorbide present in said distillate.
  • the distillate may in particular have a formic acid content of less than 0.0005% and a monoanhydrohexose content of less than 0.005%.
  • purification step b) is implemented and the gallic acid ester, and optionally the phosphate compound of the first variant or the amine of the second variant, are implemented after this step b) and they are in particular introduced directly into the purified aqueous solution of internal dehydration product resulting from step b), which generally has a temperature at most equal to 60°C.
  • the composition of internal dehydration product of a hydrogenated sugar obtained according to the invention can be shaped during a subsequent step d).
  • This step can consist of an operation of tableting or flaking of the crystallized or massaged mass resulting from the cooling, in particular by contact on a cold surface, of the composition resulting from step c).
  • the shaping step d) can, if desired, be followed by a grinding and/or sieving step, before any storage and/or bagging step of the composition as well obtained.
  • the composition of internal dehydration product of a hydrogenated sugar obtained according to the invention can, after step c), be stored as it is, in particular in the liquid or pasty state. , without any specific subsequent shaping step.
  • the resulting composition of the process according to the invention may moreover have undergone, at any time, a concentration step, in particular an evaporation step under vacuum, said step being carried out under the mildest possible conditions, in particular in terms of duration and temperature.
  • This step then consists of concentrating said composition while maintaining it in liquid form, in particular at a dry matter content of between 50 and 90%, preferably between 75 and 88%. It may also consist in concentrating said composition so as to obtain a final product in dry form.
  • step c) characteristic of the present invention and/or any subsequent step, in particular shaping, storage or bagging.
  • the expression “product of internal dehydration of a hydrogenated sugar” includes in particular the products of internal dehydration of hydrogenated sugars at C6 (hexitols) such as sorbitol, mannitol and iditol and therefore encompasses isosorbide ( 1,4 - 3,6-dianhydro-sorbitol), isomannide (1,4 - 3,6 dianhydro-mannitol), isoidide (1,4 - 3,6-dianhydro-iditol).
  • the process according to the invention is characterized in that the internal dehydration product of a hydrogenated sugar is isosorbide.
  • Another object of the present invention relates to a composition containing at least one internal dehydration product of a hydrogenated sugar, characterized in that it contains at least one gallic acid ester.
  • this gallic acid ester is chosen from alkyl esters, more preferably from ethyl gallate and propyl gallate and is still preferably propyl gallate
  • This composition is also characterized in that it contains from 0.0001 to 2%, preferably from 0.001 to 2%, more preferably from 0.002 to 1.5%, even more preferably from 0.002 to 0.1% of ester of gallic acid, these percentages being expressed as dry weight of ester of gallic acid relative to the dry weight of the product of internal dehydration of hydrogenated sugar.
  • this composition is also characterized in that it also contains a phosphate compound which is preferably disodium phosphate.
  • the composition contains from 0.0001 to 2%, preferentially from 0.001 to 2%, more preferentially from 0.002 to 1.5%, even more preferentially from 0.002 to 0.1% of said phosphate compound, these percentages being expressed as dry weight of phosphate compound relative to the dry weight of the product of internal dehydration of hydrogenated sugar
  • this composition is also characterized in that it also contains an amine which is preferably diethanolamine or triethanolamine, very preferably diethanolamine.
  • the composition contains from 0.0001 to 2%, preferentially from 0.001 to 2%, more preferentially from 0.002 to 1.5%, even more preferentially from 0.002 to 0.1% of said amine, these percentages being expressed as dry weight of amine relative to the dry weight of the product of internal dehydration of hydrogenated sugar.
  • composition in a preferred variant is characterized in that the internal dehydration product of a sugar is isosorbide.
  • composition in liquid form, it is characterized in that it has a dry matter of between 50 and 90%, preferably between 75 and 88%.
  • said composition is in solid form (said composition therefore having a dry matter content of 99 to 100%).
  • compositions can in particular be used for the preparation of products or mixtures, polymeric or not, biodegradable or not, intended for the chemical, pharmaceutical, cosmetological or food industries.
  • FIG. 1 illustrates the determination of the induction time using an oxygen consumption curve obtained according to the PetroOxy test.
  • the decrease in pressure in the enclosure of the test chamber is due to the consumption of oxygen during the oxidation reactions of the sample studied.
  • the variation in relative pressure during the experiment makes it possible to determine the time after which the sample begins to degrade (known as the induction time, OIT) under the test conditions.
  • the induction time of the solution is determined as follows:
  • the relative variation of the oxygen pressure in the enclosure, indicative of the oxygen consumption, is given by the relationship (Pt - Pmax)/Pmax, Pmax being the maximum pressure of the system over time, which corresponds to the maximum pressure during the stabilization phase, Pt is the pressure as a function of time when the oxygen is consumed.
  • the sample induction time is given by the inflection point of the oxygen consumption curve: i.e. the intersection of the two linear domains (see Fig.1).
  • Rated E in terms of antioxidant power, is determined by the difference in induction time (3 ⁇ 4) between an isosorbide solution with a stabilizer and a solution without stabilizer (isosorbide without additive, ), EFti-W
  • An additive i having a positive efficiency E will have a beneficial effect while a negative efficiency E, will testify to a deleterious effect.
  • a synergy of a mixture of additives will result in an efficiency E mixing higher than the sum of efficiencies E, of the additives of the mixture taken independently and this, with the same concentrations of the additives used.
  • Reference example preparation of an unstabilized isosorbide composition and study of its induction time.
  • An isosorbide solution is prepared as follows:
  • the reaction crude is then cooled to 100° C. then neutralized with 11.4 g of a 50% sodium hydroxide solution.
  • the isosorbide composition is distilled under vacuum (pressure less than 50 mbar).
  • the isosorbide distillate, slightly colored (light yellow) is then dissolved in isopropanol at a temperature of 60° C., so as to obtain a homogeneous solution at 75% DM. This solution is then cooled slowly, over 5 hours, to a temperature of 10°C. A recrystallized isosorbide primer is added at 40°C.
  • the crystals are then drained in a wringer and washed with isopropanol. After drying under vacuum, the crystals are redissolved in water to obtain a 50% DM aqueous solution.
  • This solution is then percolated over a column of granular activated carbon (CPG 12-40 at a relative rate of 0.5V/V/h (volume of product/volume of resin and per hour).
  • the discolored isosorbide composition thus obtained is passed at a speed of 2 V/V/h successively over a column of strong cationic resin (PUROLITE C150 S then over a strong anionic resin AM BERLITE I RA910.
  • This solution is then treated with powdered activated carbon (NORIT SX+) at 20° C. for one hour The amount of carbon used is 0.5% by weight relative to the dry weight of the solution.
  • the isosorbide solution is recovered and analyzed according to the above methodology.
  • the induction time of the isosorbide solution without additive is 5.0 h. This value will serve as a reference for determining the effectiveness of the additives.
  • Example outside the invention 1-1 preparation of an isosorbide composition with additives with disodium phosphate at 50 ppm.
  • the synthesis process is identical to Example 1 but in this case the additive used is disodium phosphate.
  • 50 mg of disodium phosphate (50 ppm) are then added to 2 kg of purified isosorbide solution (50% DM). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution supplemented with disodium phosphate at 50 ppm is 5.0 h, i.e. an efficiency E of 0.
  • the effect of this additive, at this dose, is zero on the anti isosorbide oxidant.
  • Example outside the invention 1-2 preparation of an isosorbide composition with additives with disodium phosphate at 100 ppm.
  • the synthesis process is identical to example 1 but in this case the additive used is disodium phosphate. 100 mg of disodium phosphate (100 ppm) are then added to 2 kg of purified isosorbide solution (50% DM). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with disodium phosphate at 100 ppm is 5. Oh, i.e. an efficiency E of 0.
  • the effect of this additive, at this dose, is nil on the antioxidant character of isosorbide.
  • Example outside the invention 1-3 preparation of an isosorbide composition with additives with disodium phosphate at 200 ppm.
  • the synthesis process is identical to example 1 but in this case the additive used is disodium phosphate. 200 mg of disodium phosphate (200 ppm) are then added to 2 kg of purified isosorbide solution (50% DM). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with disodium phosphate at 200 ppm is 5.1 h, i.e. an efficiency E of 0.1.
  • the effect of this additive on the antioxidant character of isosorbide is close to 0 at a dose of 200 ppm.
  • Example outside the invention 2-1 preparation of an isosorbide composition with additives with diethanolamine at 50 ppm.
  • the synthesis process is identical to Example 1 but in this case the additive used is diethanolamine at a dose of 50 mg of diethanolamine (50 ppm) are added to 2 kg of purified isosorbide solution (50 %MS). The solution is analyzed according to the methodology mentioned above.
  • Example outside the invention 2-2 preparation of an isosorbide composition with additives with diethanolamine at 100 ppm.
  • the synthesis process is identical to Example 1 but in this case the additive used is diethanolamine at a dose of 100 mg of diethanolamine (100 ppm) are added to 2 kg of purified isosorbide solution (50 %MS). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution supplemented with diethanolamine at 100 ppm is 7.2 h, i.e. an efficiency E of 2.3.
  • Example outside the invention 2-3 preparation of an isosorbide composition with additives with diethanolamine at 200 ppm.
  • the synthesis process is identical to Example 1 but in this case the additive used is diethanolamine at a dose of 200 mg of diethanolamine (200 ppm) are added to 2 kg of purified isosorbide solution (50 %MS). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with diethanolamine at 200 ppm is 7.3 h, i.e. an efficiency E of 2.3.
  • Example 3 outside the invention preparation of an isosorbide composition added with maltol at 100 ppm.
  • the synthesis process is identical to example 1 but in this case the additive used is maltol. 100 mg of maltol are then added to 2 kg of purified isosorbide solution (100 ppm). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with maltol at 100 ppm is 3.9 h, i.e. an efficiency E of -1.1 h.
  • the antioxidant power of maltol is deleterious to isosorbide.
  • Example outside the invention 4 preparation of an isosorbide composition additive with
  • the synthesis process is identical to example 1 but in this case the additive used is Trolox. 100mg of Trolox are then added to 2 kg of purified isosorbide solution (100 ppm). The solution is analyzed according to the methodology mentioned above.
  • Example outside the invention 5 preparation of an isosorbide composition with additives with gallic acid at 100 ppm.
  • the synthesis process is identical to example 1 but in this case the additive used is gallic acid. 100 mg of gallic acid are then added to 2 kg of purified isosorbide solution (100 ppm). The solution is analyzed according to the methodology mentioned above.
  • Gallic acid although similar in structure to ethyl/propyl gallate, has a negative effect on the antioxidant character of isosorbide.
  • Example 1 preparation of a composition of isosorbide additive with ethyl gallate at 50 ppm.
  • the synthesis process is identical to example 0 but in this case 50 mg of ethyl gallate are added to 2 kg of the isosorbide solution after filtration of the activated carbon (dose 50 ppm). The medium is stirred for 30 min to allow complete dissolution and guarantee the homogeneity of the solution. The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with 50 ppm ethyl gallate is 7.3 h, i.e. an efficiency E of 2.3.
  • Example 2-1 preparation of an isosorbide composition with additives with propyl gallate at 50 ppm.
  • the synthesis process is identical to example 1 but in this case the additive used is propyl gallate. 50 mg of propyl gallate are then added to 2 kg of purified isosorbide solution (dose 50 ppm). The solution is analyzed according to the methodology mentioned above.
  • Example 2-2 preparation of an isosorbide composition with additives with propyl gallate at 100 ppm.
  • the synthesis process is identical to example 1 but in this case the additive used is propyl gallate.
  • 100 mg of propyl gallate are then added to 2 kg of purified isosorbide solution (dose 100 ppm).
  • the solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with 100 ppm propyl gallate is 8.8 h, ie an efficiency E of 3.8.
  • Example 2-3 preparation of an isosorbide composition with additives with propyl gallate at 200 ppm.
  • the synthesis process is identical to example 1 but in this case the stabilizer used is propyl gallate. 200 mg of propyl gallate are then added to 2 kg of purified isosorbide solution (dose 200 ppm). The solution is analyzed according to the methodology mentioned above.
  • the induction time obtained for a solution with 200 ppm propyl gallate is 11.6 h, i.e. an efficiency E of 6.6.
  • Examples 1, 2-1, 2-2 and 2-3 indicate a very marked efficacy of ethyl gallate and especially propyl gallate on the antioxidant character of isosorbide.
  • Example 3 preparation of a composition of isosorbide stabilized with propyl gallate (100 ppm) with addition of disodium phosphate (50 ppm).
  • the synthesis process is identical to example 1 but in this case, 100 mg of propyl gallate (100 ppm) and 50 mg of disodium phosphate (50 ppm) are added to 2 kg of a solution of purified isosorbide.
  • the induction time of the solution stabilized by this mixture is 11.6 h, i.e. an efficiency of E of 6.6. This value is greater than the sum of the effectiveness of sodium phosphate at 50 ppm (0) and that of propyl gallate at 100 ppm (3.8).
  • E efficiency of E
  • Example 4 preparation of an isosorbide composition with propyl gallate (100 ppm) and diethanolamine (50 ppm).
  • the synthesis process is identical to example 1 but in this case, 100 mg of propyl gallate (100 ppm) and 50 mg of diethanolamine (50 ppm) are added to 2 kg of an isosorbide solution purified.
  • the induction time of the solution stabilized by this mixture is 13.8 h, i.e. an efficiency of E of 8.8. This value is greater than the sum of the effectiveness of diethanolamine at 50 ppm (1.2) and that of propyl gallate at 100 ppm (3.8). Without being bound by any theory, this seems to indicate a strong synergistic effect in this composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
EP22750997.3A 2021-07-28 2022-07-28 Oxidationsstabile dianhydrohexitolzusammensetzung mit gallinsäureester Pending EP4377281A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2108221A FR3125684A1 (fr) 2021-07-28 2021-07-28 Composition de dinahydrohexitols stables a l’oxydation et contenant un ester d’acide gallique
PCT/EP2022/025358 WO2023006250A1 (fr) 2021-07-28 2022-07-28 Composition de dianhydrohexitols stables a l'oxydation et contenant un ester d'acide gallique

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EP (1) EP4377281A1 (de)
KR (1) KR20240052744A (de)
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WO (1) WO2023006250A1 (de)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB613444A (en) 1946-01-17 1948-11-29 John George Mackay Bremner Improvements in and relating to the production of heterocyclic compounds
CA1178288A (en) 1982-05-07 1984-11-20 John Feldmann Process for preparing anhydro polyol containing polyol mixtures
DE3230349A1 (de) 1982-08-14 1984-02-16 Maizena Gmbh, 2000 Hamburg Verfahren zur gewinnung reiner kristalliner anhydropentite, mono- und/oder dianhydrohexite
DE3703257A1 (de) 1987-02-04 1988-08-18 Huels Chemische Werke Ag Gezielt eingestellte polyolgemische auf basis von sorbit, verfahren zu ihrer herstellung und ihre verwendung zur herstellung von sorbitanestern
FR2617846B1 (fr) 1987-07-07 1992-07-17 Beghin Say Sa Procede de preparation d'anhydrides d'hexitols, d'hexonolactones et d'hexosides
FR2810040B1 (fr) 2000-06-09 2004-04-09 Roquette Freres Procede de purification d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene
FR2832407B1 (fr) * 2001-11-20 2005-07-01 Roquette Freres Procede de preparation d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene
US20070292461A1 (en) * 2003-08-04 2007-12-20 Foamix Ltd. Oleaginous pharmaceutical and cosmetic foam
JP4370280B2 (ja) * 2005-05-16 2009-11-25 三光化学工業株式会社 無水糖アルコール組成物の精製方法および製造方法
FR3005315B1 (fr) 2013-05-02 2015-06-05 Roquette Freres Procede de stabilisation d'une composition contenant au moins un produit de deshydratation interne d'un sucre hydrogene, composition obtenue et ses utilisations

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