Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
  • C08K5/1535—Five-membered rings
• • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0016—Plasticisers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

• the invention relates to a process for preparing an alkyl diester composition of 1,4:3,6-dianydrohexitol and their use in the preparation of a polycarbonate, in particular to improve the flow of the polycarbonate in the molten state.
• alkyl diesters of 1,4:3,6-dianydrohexitol such as isosorbide can be added to a polymer to facilitate its shaping. They then play the role of “plasticizer”.
• the plasticizers mainly used at present belong to the family of phthalic esters (phthalates). Phthalates are easily available on the market at low cost, however there are attempts to replace them due to toxicity problems.
• patent EP 3 443 033 B1 describes that C8/C10 alkyl diesters of isosorbide, marketed by the Applicant company under the trade name Polysorb ID46, make it possible to facilitate the preparation of polycarbonates in particular by improving their flow in the melt state.
• the alkyl diesters of 1,4:3,6-dianydrohexitol are conventionally prepared by esterification of a 1,4:3,6-dianydrohexitol with an excess fatty acid, typically in the presence of an acid catalyst.
• the reaction crude includes unreacted fatty acid (residual fatty acid). This fatty acid having a negative effect on the use of diester compositions as a plasticizer, it is eliminated at the end of the esterification step by subjecting the reaction crude to a distillation step or a washing step by liquid-liquid comprising washing with water in the presence of a weak base such as sodium bicarbonate, the washing being followed by a drying step.
• the present invention relates to a process for preparing a composition of a C13-C29 alkyl diester of 1,4:3,6-dianydrohexitol, said process comprising: a) a first step of esterification of 1,4:3,6-dianydrohexitol with a fatty acid having a C13-C29 alkyl chain, said fatty acid being in excess, so as to form a reaction crude comprising a C13-alkyl diester C29 of 1,4:3,6-dianydrohexitol and unreacted fatty acid; b) a second step of esterification of the unreacted fatty acid with a primary or aromatic diol.
• the Applicant company has observed that when a composition obtained by esterification of 1,4:3,6-dianydrohexitol with a long-chain fatty acid is purified by distillation, the composition obtained exhibits an undesirable coloring. Concerning washing by liquid-liquid method, the Applicant company has noted that the drying step, which is applied after washing with water in the presence of a weak base, generates coloring. She also noted that in the case of saturated fatty acids, the reaction crude obtained is solid and that it is only possible to wash it at temperatures above its melting point, typically above 80°C, which generates partial hydrolysis of the 1,4:3,6-dianydrohexitol diester.
• the inventors believe that in the processes of the prior art, the risk of cleavage of the diester into monoester increases with the temperature applied during elimination by distillation or washing by liquid means - liquid, which is higher as the alkyl chain is longer.
• the inventors have developed a process in which, unlike the processes of the prior art, the elimination of the residual fatty acid does not require distillation or washing by a liquid-liquid route.
• the process according to the invention is simple to implement on an industrial and economic scale. It is based on two esterification stages carried out sequentially.
• the first step comprises the esterification of 1,4:3,6-dianydrohexitol with a long-chain fatty acid, said fatty acid being in excess, so as to obtain the maximum amount of diester.
• the second step comprises the esterification of the residual fatty acid with a primary or aromatic diol so as to eliminate most, almost all, or even all of the fatty acid which has not reacted during of the first esterification step.
• This elimination by esterification has the advantage of being simpler to implement than elimination by distillation and of being able to be implemented directly in the esterification reactor than that used in the first esterification step. .
• the process according to the invention is therefore advantageously a one-pot process, that is to say a preparation process whose steps are carried out successively in the same reactor.
• the process according to the invention advantageously does not include an isolation, separation or purification step by evaporation, for example by distillation.
• compositions obtained according to the process according to the invention have low colorings and are effective in polycarbonate preparation processes.
• C13-C29 alkyl diester is meant an alkyl diester of 1,4:3,6-dianydrohexitol in which alkyl groups are linked to the hydroxyl groups of 1,4:3,6-dianydrohexitol.
• This C13-C29 alkyl diester is produced by esterification reaction of 1,4:3,6-dianhydrohexitol with a fatty acid.
• the alkyl group of the ester is R' and is therefore a C13 alkyl group.
• the ester is a monoester. It is a diester in the case where the two alcohol functions of the diol have reacted in an esterification reaction.
• the C13-C29 alkyl diester of 1,4:3,6-dianhydrohexitol may comprise different alkyl groups when the diester is obtained with 2 different fatty acids
• fatty acid having a C13-C29 alkyl chain designates an R'-COOH fatty acid comprising 14 to 30 carbon atoms, a carbon atom belonging to the carboxylic acid group (-COOH), the remainder of the carbon atoms belonging to a substituted or unsubstituted linear or branched alkyl chain, comprising between 13 and 29 carbon atoms, or one of their mixtures.
• the alkyl chain is preferably saturated.
• the alkyl chain can be substituted by at least one group comprising a heteroatom chosen from oxygen and nitrogen, preferably by a ketone or hydroxyl group or by an amine group.
• the chain can be substituted at the end of the alkyl chain by a cyclic group typically containing from 5 to 12 carbon atoms, preferably from 6 to 10 carbon atoms, preferably by a cyclohexane or cyclopentane cycle, or by an alkyl chain in C2-C4 linked to the alkyl chain of the fatty acid at two attachment points so as to form an intra-chain ring, preferably an intra-chain cyclopropane.
• a 1,4:3,6-dianydrohexitol is esterified with a fatty acid having a C13-C29 alkyl chain.
• 1,4:3,6-dianhydrohexitol is a diol of the chemical formula C 6 Hio0 4 .
• isosorbide isomannide and isoidide, or one of their mixtures.
• Isosorbide is preferred.
• the fatty acid preferably has a C13-C29, preferably C13-C17, alkyl chain.
• the fatty acid can be chosen from stearic acid (C18:0 octadecanoic acid), myristic acid (C14:0 tetradecanoic acid), palmitic acid (C16 hexadecanoic acid: 0), isopalmitic acid (14-methylpentadecanoic acid), margaric acid (heptadecanoic acid C17:0), tuberculostearic acid (10-methylstearic acid), lactobacillic acid (10-[(1 R,2S) -2- hexylcyclopropyl]decanoic), arachidic acid (icosanoic acid C20:0), acid phytanic acid (3,7,11,15-tetramethylhexadecanoic acid), 11-cyclohexylundecanoic acid (11-cyclohexylundecanoic acid) or a mixture thereof.
• stearic acid C18:0 octadecano
• the fatty acid is advantageously a C16 or C18 fatty acid, or one of their mixtures.
• the fatty acid having a C13-C29 alkyl chain is in excess relative to the 1,4:3,6-dianydrohexitol in order to promote the formation of the C13-C29 alkyl diester of 1,4:3,6-dianydrohexitol and to minimize the formation of the corresponding monoester.
• 2y+z moles of fatty acid are preferably reacted for y moles of 1,4:3,6-dianydrohexitol, with y and z in moles, 2y representing the stoichiometric quantity of fatty acid relative to y mole of 1,4:3,6-dianydrohexitol, and z representing the quantity of fatty acid which is in excess relative to said stoichiometric quantity.
• the stoichiometric excess of the fatty acid relative to 1,4:3,6-dianydrohexitol can also be expressed as a percentage using the formula (z/2y+z)x100.
• the fatty acid is preferably in stoichiometric excess of 10% to 100% relative to 1,4:3,6-dianydrohexitol.
• the 1,4:3,6-dianydrohexitol is preferably reacted with the fatty acid in a 1,4:3,6-dianydrohexitol/fatty acid molar ratio of between 1/2.2 and 1/4.
• reaction crude means the product of the first step of esterification of 1,4:3,6-dianydrohexitol with a fatty acid having a C13-C29 alkyl chain, and to which has preferably not been applied any step of elimination of residual fatty acids, in particular no step of isolation, separation or purification, in particular no step of elimination of fatty acids which have not reacted by distillation or by liquid-liquid route.
• the reaction crude preferably comprises an alkyl diester of 1,4:3,6-dianydrohexitol, an alkyl monoester of 1,4:3,6-dianydrohexitol and fatty acid having no reacted.
• the fatty acid which did not react during the first step is esterified with a primary or aromatic diol, in order to eliminate as much of this fatty acid as possible from the reaction crude.
• the primary or aromatic diol has greater reactivity than 1,4:3,6-dianydrohexitol of step a). Preferably, it does not transesterify with the C13-C29 alkyl diester of 1,4:3,6-dianydrohexitol of the reaction crude obtained at the end of step a).
• diol is meant a compound comprising two hydroxyl groups (-OH).
• the compound is preferably a hydrocarbon structure typically comprising between 2 and 20 carbon atoms, preferably between 2 and 12 carbon atoms.
• the diol used in step b) is a primary or aromatic diol.
• primary diol is meant a diol whose hydroxyl groups are carried by a carbon atom also carrying at least 2 hydrogen atoms.
• aromatic diol is meant a diol whose hydroxyl groups are carried by a carbon atom of an aromatic ring.
• aromatic cycle is meant a polyunsaturated cyclic hydrocarbon structure in which the cyclic structure is planar and has (4n + 2) delocalized electrons, n being an integer, having a single cycle or several cycles condensed together and typically containing from 5 to 12 carbon atoms, preferably from 6 to 10 carbon atoms.
• a preferred aromatic ring is phenyl.
• the primary diol preferably comprises from 2 to 20 carbon atoms, preferably from 2 to 15 carbon atoms.
• the primary or aromatic diol can be chosen from ethylene glycol, cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), 1,4-butanediol, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, resorcinol, 1,5-pentanediol, 1,6 hexanediol, 1,8 octanediol, 1,10 decandiol, 1,12 dodecanediol or mixtures thereof.
• CHDM cyclohexanedimethanol
• NPG neopentyl glycol
• 1,4-butanediol 1,2-benzenedimethanol
• 1,3-benzenedimethanol 1,4-benzenedimethanol
• resorcinol 1,5-pentanediol
• 1,6 hexanediol 1,8 octanediol
• Ethylene glycol is preferred.
• the primary or aromatic diol is preferably introduced in stoichiometric proportions or in slight deficiency relative to the fatty acid which has not reacted during the first step, in order to eliminate the quasi -all of this fatty acid.
• the inventors consider that if the primary or aromatic diol is added in stoichiometric excess relative to the residual fatty acid, the final composition presents a risk of containing monoester of this primary or aromatic diol, which leads to a risk of transesterification and therefore generation of 1,4:3,6-dianydrohexitol monoester.
• primary or aromatic diol with a slight defect in relation to the fatty acid which has not reacted during the first step we mean a stoichiometric defect, that is to say a quantity of primary or aromatic diol slightly lower than the stoichiometric quantity necessary for the esterification reaction of all the hydroxyl groups of the fatty acid not reacted during the first step.
• step a) is carried out with a mole quantity of fatty acid which is in excess compared to the stoichiometric quantity (which can be denoted "z", as detailed below).
• step b) is carried out with a mole quantity of primary diol which corresponds to between 45% and 50% of the mole quantity of fatty acid used in excess compared to the quantity stoichiometric during step a).
• esterification steps can be carried out under the standard implementation conditions already used in the literature. These esterification methods are described for example in documents WO 99/45060 A1 or WO 2006/103338 A1.
• the esterification steps are preferably carried out in the presence of at least one acid catalyst.
• the acid catalyst used can be of a very varied nature, for example can be an acid catalyst chosen from hypophosphorous acid, hydrochloric acid, sulfuric acid, para-toluene sulfonic acid (APTS) , methanesulfonic acid (AMS), trifluoromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, ethyl- Tin 2-hexanoate, phosphotungstic acid and silicotungstic acid or a mixture of these acids or a macroporous or non-macroporous resin comprising at least one of these acids.
• an acid catalyst chosen from hypophosphorous acid, hydrochloric acid, sulfuric acid, para-toluene sulfonic acid (APTS) , methanesulfonic acid (AMS), trifluoromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, ethyl- Tin 2-hexanoate, phosphotungstic acid and
• the mass quantity of acid catalyst can range from 0.05 to 20% relative to the mass of 1,4:3,6-dianhydrohexitol introduced into the reactor, for example from 0.1 to 10%.
• hypophosphorous acid can also act as a color reducer.
• This can be introduced into the reaction medium simultaneously or not with another acid catalyst and/or with the fatty acid. According to one variant, this introduction is carried out before or from the start of the esterification reaction, i.e. before the introduction of the acid catalyst and/or the fatty acid.
• the hypophosphorous acid is introduced in a quantity of between 0.05 and 2%, preferably between 0.1 and 1%, expressed in dry weight relative to the weight. dry of 1,4:3,6-dianydrohexitol(s) used.
• the hypophosphorous acid is introduced, simultaneously or not with the acid esterification catalyst, in a hypophosphorous acid/acid catalyst ratio of less than 1/1, said ratio being expressed in dry weight of hypophosphorous acid relative to the weight. dry of acid catalyst.
• Said ratio may in particular be between 0.01/1 and 0.9/1, preferably between 0.02/1 and 0.8/1.
• the catalyst is APTS, methanesulfonic acid or phosphotungstic acid, said ratio can advantageously be between 0.05/1 and 0.4/1.
• the temperature in the reactor can range from 90 to 200°C, generally from 100 to 160°C.
• the water is generally eliminated in order to promote the formation of the diester, this elimination being able to be done for example by distillation of the reaction medium.
• the reaction medium can be placed under vacuum, for example at a level ranging from 10 to 200 mbar. Reaction conditions such as vacuum level and temperature can be varied during the reaction.
• the first esterification step generally lasts the time to obtain a satisfactory conversion to 1,4:3,6-dianhydrohexitol diester. It can vary widely and range from 1 to 10 hours.
• the second esterification step generally lasts long enough to obtain satisfactory elimination of the free fatty acid. It can vary widely and range from 1 to 10 hours.
• a step of neutralizing the catalyst introduced by introducing a base, for example sodium hydroxide, in molar quantities equivalent to the molar quantities of catalyst introduced.
• This neutralization step is preferably carried out after the second esterification step.
• the process according to the invention may also comprise a step of decolorization of the reaction crude resulting from step a) using color reducers, for example activated carbon or hydrogen peroxide, or even bleaching earths. such as bleaching clay, bentonite or montmorillonite.
• color reducers for example activated carbon or hydrogen peroxide, or even bleaching earths.
• bleaching earths such as bleaching clay, bentonite or montmorillonite.
• This step can be carried out successively in one of steps a) and/or b).
• the bleaching agents are added at the end of one of steps a) and/or b).
• This step can also be carried out simultaneously with steps a) and/or b).
• the bleaching agents are added at the start of one or each of steps a) and/or b).
• the treatment with activated carbon is carried out for example by bringing the reaction crude into contact with 1 to 5% by weight of activated carbon.
• the temperature during this treatment can be close to 100°C.
• the duration is generally several tens of minutes, for example for about an hour.
• the activated carbon is separated by filtration.
• the treatment is similar to treatment with activated carbon.
• a conventional bleaching treatment with hydrogen peroxide consists for example of introducing into the composition to be bleached, over a period ranging for example from 30 to 60 minutes, from 0.5 to 2% of 100% hydrogen peroxide, at a temperature between 90°C and 100°C, then the composition is stirred for one to two hours at this temperature.
• the treatment with hydrogen peroxide preferably precedes that with activated carbon.
• the process according to the invention allows the preparation of a composition of a C13-C29 alkyl diester of isosorbide, said process comprising: a) a first esterification step of isosorbide with a fatty acid having an excess C13-C29 alkyl chain, for example in an isosorbide/fatty acid molar ratio of between 1/2.3 and 1/3 so as to form a reaction crude comprising a diester of isosorbide alkyl and unreacted fatty acid; b) a second step of esterification of the unreacted fatty acid with a primary or aromatic diol, preferably with ethylene glycol, in which the fatty acid having a C13-C29 alkyl chain is preferably a fatty acid having a C13, C14, C15, C16, C17 or C18 alkyl chain.
• a second subject of the invention relates to a C13-C29 alkyl diester composition of 1,4:3,6-dianydrohexitol capable of being obtained by the process of the first subject of the invention.
• diester composition is obtained from different 1,4:3,6-dianydrohexitols, different primary and/or aromatic diols, and/or different fatty acids having a C13-alkyl chain C29, very complex and diverse compositions are obtained which cannot be defined more satisfactorily than by the preparation process.
• compositions according to the invention can be defined relatively easily when a limited number of 1,4:3,6-dianydrohexitol(s), primary and/or aromatic diol(s) are used. s), and/or fatty acid having a C13-C29 alkyl chain.
• a third subject of the invention relates to a C13-C29 alkyl diester composition
• a C13-C29 alkyl diester composition comprising, by composition weight: from 35 to 85% of a C13-C29 alkyl diester of 1, 4:3,6-dianydrohexitol (A), from 10 to 50%, % of diester of a primary or aromatic diol (B), less than 6% of C13-C29 alkyl monoester of 1,4: 3,6-dianydrohexitol (C), less than 3% fatty acid having a C13-C29 alkyl chain (D), the total content of C13-C29 alkyl diester of 1,4:3,6-dianydrohexitol (A) and diester of a primary or aromatic diol (B) being between 80% and 99%, preferably between 90 and 99%.
• the total content of C13-C29 alkyl diester of 1,4:3,6-dianydrohexitol (A) and diester of a primary or aromatic diol (B) being between 80% and 99%, preferably between 90 and 99%.
• 1,4:3,6-dianydrohexitol, the primary or aromatic diol, the fatty acid, and the esters are as defined in the first subject of the invention.
• composition according to the invention has the advantage of being lightly colored.
• compositions comprising a mixture of C13-C29 alkyl diester of 1,4:3,6-dianydrohexitol and diester of a primary or aromatic diol present performances equivalent or even superior to compositions obtained by eliminating the residual fatty acid in accordance with the processes of the prior art, by distillation or by liquid-liquid washing, and therefore comprising only one or more alkyl diesters of 1,4:3,6-dianydrohexitol, but not a diester of a primary or aromatic diol.
• composition according to the invention preferably comprises 50 to 85% diester (A).
• composition according to the invention preferably comprises 10 to 50%, more preferably 10 to 35% of diester (B).
• composition according to the invention preferably comprises less than 5%, 4%, 3%, or less than 2% of monoester (G), typically 0.5 to 6%, typically still 2 to 6%. of monoester (C).
• composition according to the invention preferably comprises less than 2% or 1% of fatty acid (D), typically 0.5 to 3%, typically still 1 to 3% of fatty acid (D). .
• 1,4:3,6-dianydrohexitol is preferably isosorbide.
• the alkyl diester is C13-C17 and the fatty acid has a C13-C17 alkyl chain.
• the primary or aromatic diol is preferably ethylene glycol.
• the composition according to the invention comprises, by composition weight: 35 to 85% isosorbide distearate (A), 10 to 50% ethylene glycol distearate (B), less than 6% isosorbide monostearate (C), less than 3% stearic acid .
• the composition according to the invention comprises, by weight of composition: from 35 to 85% of isosorbide dimyristate (A), from 10 to 50% of ethylene glycol dimyristate (B ), less than 6% isosorbide monomyristate (C), less than 3% myristic acid.
• esters and fatty acids can be determined by usual methods known to those skilled in the art, typically by gas phase chromatography or HPLC.
• composition may also comprise traces of monoester of a primary or aromatic diol (E), for example from 0 to 1%, preferably from 0 to 0.1% of monoester (E), by weight of composition.
• E monoester of a primary or aromatic diol
• composition may also comprise traces, for example from 0 to 1%, preferably from 0 to 0.1%, more preferably from 0 to 0.01% of primary or aromatic diol (F), by weight. decomposition.
• traces for example from 0 to 1%, preferably from 0 to 0.1%, more preferably from 0 to 0.01% of primary or aromatic diol (F), by weight. decomposition.
• esters (A), (B), (C), (E), fatty acids (D) and primary or aromatic diol (F) is preferably equal to 100%.
• composition advantageously has an APHA coloring index of less than 30.
• the APHA coloring index of the composition according to the invention is preferably between 10 and 30, more preferably between 15 and 25, more preferably between 18 and 22.
• composition according to the invention is particularly advantageous for use of the composition according to the invention as an additive, typically as a flow agent in the manufacture of a transparent synthetic polymer such as a polycarbonate.
• the measurement of the APHA coloring index is carried out directly on a sample of the composition according to the procedure of standard ASTM D8005-18 of March 2018. It should be noted that certain compositions can be present in the form of a solid having a melting point of approximately 80°C. In this case, the coloring index is measured according to the procedure of standard ASTM D8005-18 of March 2018 except that the measurement is carried out at a temperature of 90°C (ie higher than the melting point of the composition ) so that the composition is in liquid form.
• a third object of the invention concerns the use of a composition according to the second or third object of the invention in a process for preparing a synthetic polymer.
• plasticizer we generally mean a product which, when mixed in sufficient quantity with a polymer, facilitates its shaping, for example by reducing the glass transition temperature of said polymer.
• composition according to the second or third object of the invention is particularly suitable for the preparation of transparent synthetic polymers, in which color is an issue, such as polycarbonate.
• composition according to the second or third object of the invention is preferably used in a process for preparing a polycarbonate, in particular during the shaping of a polycarbonate, to improve the flow of the melt. .
• the process for preparing polycarbonate comprises at least one step of shaping a polycarbonate by extruding a mixture comprising a diester composition according to the second or third object of the invention with a polycarbonate, the mixture typically containing between 3 and 5% by weight of composition according to the second or third object of the invention.
• the polycarbonate may be an aliphatic polycarbonate or an aromatic polycarbonate.
• the polycarbonate can be an aromatic polycarbonate typically such as those described in patent EP 3 443 033 B1.
• the aromatic polycarbonate is preferably an aromatic polycarbonate containing monomer units of formula -[CO-O-pR1-R2-pR1 -O] n , in which R1 represents a phenyl optionally substituted by a C1-C4 alkyl; R2 represents a group R3(R4R5), with R3 a carbon atom or a ring of 6 carbon atoms and R4 and R5, which may be the same or different from each other, each represent a hydrogen atom or a group ( R6)n, in which R6 represents a C1-C4 alkyl, n representing 1, 2 or 3.
• each ester is measured by gas phase chromatography on Varian 3400 type equipment with FID detection and split/splitless type 1077 injector.
• the column used is a J & W Scientific brand DB1, 30 meters long, internal diameter 0.32 mm, film thickness 0.25 mm.
• the temperature conditions are: injector and detector: 300°C; column: programming from 100°C to 320°C at a rate of 7°C/min, maintained for 15 mins at 320°C.
• the injection is done in split at 80 ml/min, the pressure at the top of the column being 14 psi and the carrier gas used is helium.
• the relative quantity of diester is given by the ratio of the sum of the areas of the compounds corresponding to the isosorbide diesters relative to an external standard, heptadecanoic acid.
• the APHA coloring index is measured according to the procedure of standard ASTM D8005-18 of March 2018.
• Example 1 Synthesis of isosorbide distearate followed by esterification of residual fatty acids by addition of ethylene glycol (ACCORDING TO THE INVENTION)
• the medium is then cooled to 100° C. and brought back under nitrogen and a stoichiometric quantity of sodium hydroxide was added to neutralize the AMS and the hypophosphorous acid.
• the reaction medium is filtered hot (100°C) on a Beko KD3 filter. The results are as follows (relative % in the composition relative to the total weight of the composition).
• the reaction crude was distilled on a scraped film evaporator (distillation surface: 0.0045m 2 ) at 190°C under vacuum at 0.1 mbars and at an introduction flow rate of 1 Kg/h in order to distill excess fatty acid.
• the composition of diester in the residue is as follows (relative % in the composition relative to the total weight of the composition):
• Example 3 Variation in the excess fatty acid of (Example 1 (ACCORDING TO THE INVENTION)
• the medium is then cooled to 100° C. and a stoichiometric quantity of sodium hydroxide is added to neutralize the AMS and the hypophosphorous acid.
• the reaction medium is filtered hot (100°C) on a Beko KD3 filter. The results are as follows (relative % in the composition compared to the total weight of the composition):
• the medium is heated to 160°C and a vacuum ramp is then applied, from 100mbar to 5mbar in 4 hours. [0111] The medium is then cooled to 100° C. and a stoichiometric quantity of sodium hydroxide is added to neutralize the AMS and the hypophosphorous acid. The reaction medium is filtered hot (100°C) on a Beko KD3 filter. The following results are obtained (relative % in the composition):
• Example 1 was reproduced by replacing stearic acid with myristic acid. (C14:0). The results are as follows:
• composition of the medium is as follows (relative % in the composition relative to the total weight of the composition):
• Example 2 A comparative example identical to Example 2 was carried out except that the stearic acid (C18:0) is replaced by myristic acid (C14:0).
• the results after distillation are as follows (relative % in the composition relative to the total weight of the composition):
• Example 7 (ACCORDING TO THE INVENTION) [0116]
• Example 2 was reproduced by replacing ethylene glycol with cyclohexanedimethanol (CHDM). The results are as follows (relative % in the composition compared to the total weight of the composition):
• Example 2 was reproduced by replacing ethylene glycol with neopentyl glycol (NPG). The results are as follows (relative % in the composition compared to the total weight of the composition):
• Example 2 was reproduced by replacing ethylene glycol with 1,4-butanediol. The results are as follows (relative % in the composition compared to the total weight of the composition):
• Example 2 was reproduced by replacing ethylene glycol with 1,4-benzenedimethanol. The results are as follows (relative % in the composition compared to the total weight of the composition):
• Example 2 was reproduced by replacing ethylene glycol with resorcinol. The results are as follows (relative % in the composition compared to the total weight of the composition):
• Example 12 Use in a polycarbonate preparation process (ACCORDING TO THE INVENTION)
• a mixture comprising polycarbonate and approximately 0.5% of a diester composition, % by weight of mixture, was extruded.
• compositions of Examples 1, 3, 5 and 7 to 11 have proven effective in improving the flow of polycarbonate melt.
• the melt flow index (MFI) was determined according to the ISO 1133 standard on a dedicated device (brand CEAST, model 7024).
• Non-additive extruded polycarbonate has an MFI of 12.9g/10min.
• the same polycarbonate added to 0.5% of the composition from Example 1 has an MFI of 43.5g/10min.
• the same polycarbonate added to 0.5% of the composition from Example 3 has an MFI of 42.75g/10min.
• Example 13 Use in a polycarbonate preparation process (COMPARATIVE)
• a C8/C10 alkyl diester composition of isosorbide marketed by the Applicant company under the name Polysorb ID46 was used in a process for preparing polycarbonate.
• the polycarbonate obtained after extrusion has an undesirable yellow color.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2022
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