EP1515980A1 - Trans-acidolysis process for the preparation of surface-active carbohydrate fatty-acid esters - Google Patents

Trans-acidolysis process for the preparation of surface-active carbohydrate fatty-acid esters

Info

Publication number
EP1515980A1
EP1515980A1 EP02733770A EP02733770A EP1515980A1 EP 1515980 A1 EP1515980 A1 EP 1515980A1 EP 02733770 A EP02733770 A EP 02733770A EP 02733770 A EP02733770 A EP 02733770A EP 1515980 A1 EP1515980 A1 EP 1515980A1
Authority
EP
European Patent Office
Prior art keywords
carbohydrate
fatty
acid
unreacted
acid esters
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Withdrawn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
EP02733770A
Other languages
German (de)
English (en)
French (fr)
Inventor
Olobo Jonathan Obaje
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.)
Urah Resources (Nigeria) Ltd
Original Assignee
Urah Resources (Nigeria) Ltd
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 Urah Resources (Nigeria) Ltd filed Critical Urah Resources (Nigeria) Ltd
Priority claimed from PCT/SG2002/000133 external-priority patent/WO2004002997A1/en
Publication of EP1515980A1 publication Critical patent/EP1515980A1/en
Withdrawn legal-status Critical Current

Links

Definitions

  • the present invention relates to process for production of surface- active carbohydrate fatty-acid esters, in particular, a low temperature, solvent-free trans-acidolysis reaction between carbohydrate ester of low molecular-weight carboxylic acid and free fatty acid under reduced pressure and in the present of acid catalyst.
  • Carbohydrate fatty-acid esters are non-irritant, nonionic surfactants with excellent biodegradability properties. They are used to solubilize membrane proteins and to formulate many grades of detergents, pharmaceutical, food and cosmetic products. Carbohydrate fatty-acid esters are also used as therapeutic agents.
  • Carbohydrate esters can also be used for treating gallstones (U.S. Pat. No. 4,264,583), colonic disorders (U.S. Pat. No. 5,840,860) and hypercholesterolemia (U.S. Pat.
  • Mutual solvents such as pyridine, N, N-dimethylformamide (DMF), dimethylacetamide (DMA), dimethylsulfoxide (DMSO), chloroform, benzene and toluene, are required to solubilize the substrates. These mutual solvents are toxic and cannot be removed to the level compatible with current regulations, thus limiting product applications.
  • U.S. Patent No. 5,945,519 describes a process for the solvent-free preparation of sucrose fatty acid esters and their mixtures with nonsugar polyol fatty acid esters.
  • a sucrose is reacted with one or more fatty acid alkyl esters of a chain length of 6 to 20 carbon atoms at temperatures between 1 20 to 1 60 degree C and the reaction mixture is then reacted at reduced pressure with fatty acid alkyl ester, and then filtered without addition of solvent.
  • 4,996,309 discloses a process for preparing sucrose fatty acid esters by reacting sucrose and a fatty acid alkyl ester in an aqueous reaction system in the presence of an alkaline catalyst.
  • the catalyst introduces large amounts of soap in the product. Separation and purification is thus made cumbersome and expensive, involving a reverse osmosis and an ultrafiltration step. Even then, only 70% product purity is normally attainable.
  • US Patent No. 5,872,245 describe a continuous process for the synthesis of sucrose fatty acid esters by reacting sucrose in limited amount of methanol, as "carrier” solvent, with fatty acid methyl ester in the presence of stationary transesterification catalyst and mechanical emulsification.
  • the process employs heavy metal catalysts, such as Zn, Cu, Sn and Pb, in addition to catalytic amount of sodium hydroxide. Product separation is achieved by density differentiations.
  • the process does not however address the color and antifacts introduced by the presence of sodium hydroxide and heat. Moreover, the effective density differentiation of the product mixture of more-than-six similar products and reactants results in a long holdup time in the process cycle. The formation of mono-, di-, tri- and polyester cannot be selectively controlled, there is therefore a stockpile of "over esterified" polyols formed in the process.
  • the present invention provides a trans-acidolysis process for preparing surface-active carbohydrate fatty-acid esters, comprising a low temperature, trans-acidolysis reaction between carbohydrate ester of low molecular-weight carboxylic acid (C2 or C3) and free fatty acid (C6 to C22) under reduced pressure and in the presence of an acid catalyst.
  • carbohydrate ester of low molecular-weight carboxylic acid C2 or C3
  • free fatty acid C6 to C22
  • the invention provides a solvent-free trans-acidolysis process for preparing surface-active carbohydrate fatty-acid esters comprising the steps of: (a) reacting acylated carbohydrate with free fatty acid in the presence of an acid catalyst, under reduced pressure;
  • step (b) decolorizing and extracting or crystallizing out the unreacted fatty acid, from the reaction mixture obtained in step (a), for recycle;
  • step (c) precipitating out the unreacted acylated carbohydrate from the reaction mixture obtained in step (a), for recycle;
  • step (a) is carried out with no solvent added to the reaction mixture.
  • the reaction is preferably performed at a temperature range of 60 to 95 degree C.
  • the precipitation of the unreacted acylated carbohydrate in step (c) may be achieved by cooling the carbohydrate fatty acid ester layer to a temperature between -4 and 10 degree C.
  • mono-, di- and poly-fatty esters of C2 or C3-acylated carbohydrates may be obtained depending on the degree of substitution and chain-length of the fatty acid moiety.
  • carbohydrate fatty esters with free hydroxyl groups of HLB values 8-16 may be obtained by a further step of partial hydrolysis in the presence of an acid catalyst.
  • the unreacted free fatty acids and the unreacted carbohydrate esters of low molecular-weight carboxylic acids are removed during purification, and recycled to the starting reactant mixture.
  • the C2- or C3- acyl group attached to the reactant carbohydrate is a good protecting and leaving group and, at the same time, enhances the solubility of the carbohydrate moiety in the fatty acid;
  • the invention is applicable to both batch-wise and continuous carbohydrate fatty ester processes.
  • This process is adaptable for producing a number carbohydrate fatty acid esters.
  • Figure 1 is a process flow diagram of a preferred embodiment of the present invention.
  • Figure 2 is a graph of HLB profiles of product carbohydrate fatty acid esters before and after deacylation.
  • the preferred reactant C2- or C3- acylated carbohydrates includes mono to trisaccharide carbohydrates, and the preferred free fatty acids includes C6-C22 chain-length, with zero, mono or di-unsaturations.
  • the acid catalysts includes sulphuric acid and camphorsulfonic acid, in the case of the monosaccharides; and boron trifluoride diethyl etherate, alkyl sulphonic acid polysiloxanes and tosylic acid, in the case of the di- and tri-saccharides.
  • the carbohydrate fatty ester of the present process has the following chemical structures:
  • R2, R3, R5 are each selected from the group consisting of H, CHaCO, CH3CH2CO, and C6-C22 fatty acyl group
  • R1 , and R4 are each selected from the group consisting of a partially or peracylated mono- or di-saccharide, H, CH3CO, CH3CH2CO or C6-C22 fatty acyl group
  • n is an integer with value equal to 1 , 2, or 3; wherein the primary monosaccharide unit could be a furanosyl, pyranosyl or a C2-C6 open- chain structure.
  • a 10 (preferably, mono to tri-saccharide) is reacted with a C6-C22 free fatty acid (Reactant B 1 1 ) in reactor 1 (1 2).
  • the reaction is carried out in the presence of an acid catalyst, with continuous stirring at a temperature range from 60 to 95 degree C (preferably from 80 to 90 degree C for the monosaccharides and 60 to 75 degree C for the di- and trisacchrides), under reduced pressure ranging from 4 to 20 Torr, (preferably from 5 to
  • reaction is continued for 3-6 hours after which it is then stopped and the reaction mixture is then taken up in an organic solvent such as iso-propanol, n-propanol, ethyl acetate or ethanol.
  • organic solvent such as iso-propanol, n-propanol, ethyl acetate or ethanol.
  • the low molecular weight C2- or C3-carboxylic acid which is a byproduct of the trans-acidolysis, is trapped by condensation and kept for other uses.
  • Step 2 The reaction mixture is then passed onto a decoloriser 1 3 where it is decolorized by contact with an adsorbent, such as activated carbon, and then filtered.
  • an adsorbent such as activated carbon
  • the unreacted free fatty acid (Reactant B 1 1 ) and the unreacted acylated carbohydrate (Reactant A 10) may then be recovered and recycled by either step 3 or step 4 as described below:
  • step 2 The solvent in step 2 is removed by vacuum distillation, in the distiller 1 5, at temperature between 30 and 50 degree C and the unreacted fatty acid is then extracted with hexane. Hexane is then vacuum distilled, at temperature between 30 and 50 degree C, to recover the unreacted fatty acid.
  • the remaining reaction mixture is redissolved in the solvent used in Step 2 to form 30 - 40% w/v solution and cool to -4 to 10 degree C in the chiller separator 1 4 to give unreacted acylated carbohydrate precipitate.
  • the filtrate solvent is then vacuum distilled off to give product acylated carbohydrate fatty esters
  • the unreacted fatty acid is crystallized out by spiking the solvent in step 2 with 10 -20 % V/V water and cooling the solution to between 8 to 1 2 degree C in the chiller separator 14.
  • the unreacted acylated carbohydrate is then removed as precipitate by cooling the solution further to between -4 and 0 degree C.
  • the filtrate solvent is then vacuum distilled off to give product acylated carbohydrate fatty esters (Product A 1 6).
  • the recovered unreacted fatty acid and acylated carbohydrate are kept for recycle into reactor 1 (1 2).
  • the acylated carbohydrate fatty ester (Product A 16) obtained in Step 3 or 4 may be passed onto a second reactor (Reactor 2 (1 7)), wherein free hydroxyl groups are librated by partial hydrolysis in the presence of an acid catalyst (Reactant C 1 8) to produce the required HLB profile depending on the degree of substitution, deacylation and chain length of the fatty acyl group. Details of the HLB profile of products are given in Figure 2.
  • the free fatty acid which may be librated during hydrolysis, is removed by crystallization in the Stage Cooler / Separator 19 and recycled to reactor 1 (1 2).
  • products having distinct HLB values may be produced, as detailed in Figure 2. These products have varying solubilities and sublimation temperatures and are thus separated into carbohydrate fatty acid esters by staged cooling between the temperatures of 10 and - 1 5 degree C, depending on the esters present.
  • the product may then be passed through quality assurance and onto the former to give the desired form such as pellets, flakes, powder, paste or liquid for supply to downstream users.
  • EXAMPLE 1 Preparation of acetylated glucose laurate and the partially deacylated glucose laurate
  • unreacted fatty acid is crystallized out by spiking the n-propanol solution with 10 -20 % V/V water and cooling the solution to between 8 to 1 2 degree C, and then removing the unreacted GPA as precipitate by cooling the solution further to between -4 and 0 degree C.
  • acetylated glucose laurate obtained above was added to CF3COOH:H2 ⁇ (7:3) to form a 20 - 50% w/v solution and agitated for a duration of time between 1 5 minutes to 2 hours, at room temperature (22 - 33 degree C).
  • the solvent was distilled off under reduced pressure.
  • the product is separated into carbohydrate fatty acid esters of varying degree of deacylation and or substitution by staged cooling between the temperatures of 10 and - 1 5 degree C.
  • Example 2 Preparation of acetylated sucrose oleate and the partially deacylated sucrose oleate
  • 0.06mol (1 6.93g) of oleic acid (Fluka Chemika, Switzerland) was weighed into a three-necked, round-bottom flask equipped with a magnetic stirrer, stopcocks, a vacuum take-off line leading to a liquid nitrogen cold-trap and a vacuum pump.
  • 0.01 mol (6.79g) of sucrose octaacetate, SOA, (Fluka Chemika, Switzerland) was added and the mixture was heated to 80 -95 degree C in an oil bath with continuous stirring until a homogenous solution was formed.
  • 0.01 % w/w tosylic acid (or alkyl sulfonic acid polysiloxane, or BF3.0Et 2 ) was then added.
  • Reaction temperature was then reduced to between 60 -75 degree C and 5-10 Torr pressure was applied. The reaction was continued for 3 to 6 hours.
  • the product was taken up in 250ml of iso-propanol, neutralized with aqueous 1 M NaHC ⁇ 3, decolourised with 2.0g activated charcoal, and filtered. Iso-propanol was then removed by vacuum distillation.
  • Unreacted oleic acid was extracted with 50x4 ml hexane and kept for reuse.
  • the sucrose fatty ester was redissolved in warm iso-propanol to form 30 - 40% w/v solution, cool to -4 to 0 degree C and filtered to give unreacted SOA as precipitate.
  • the filtrate iso-propanol was then distilled off to give 70-85% pure acetylated sucrose oleate. Repeated hexane extraction and SOA precipitation gave 90-95% pure product (87% yield).
  • acetylated sucrose oleate obtained above was added to CF 3 COOH:H 2 0 (7:3) to form 20 - 50% w/v solution and agitated for a duration of time between 1 5 minutes to 2 hours, at room temperature (22 - 33 degree C).
  • the solvent was distilled off under reduced pressure. If desirable, the product is separated into carbohydrate fatty acid esters of varying degree of deacylation and or substitution by staged cooling between the temperatures of 10 and - 1 5 degree C.
  • 0.06mol (1 2.0g) of lauric acid (Fluka Chemika, Switzerland) was weighed into a three-necked, round-bottom flask equipped with a magnetic stirrer, stopcocks, a vacuum take-off line leading to a liquid nitrogen cold-trap and a vacuum pump.
  • 0.01 mol (1 1 .54g) of raffinose peracetate, RA (prepared above) was added and the mixture was heated to 80-100 degree C in an oil bath with continuous stirring until a homogenous solution was formed.
  • 0.01 % w/w BF3.0Et2 or tosylic acid or alkyl sulfonic acid polysiloxane
  • Reaction temperature was reduced to between 60and 75 degree C and 5 -10 Torr pressure was applied. The reaction was continued for 2 to 6 hours. The product was taken up in 250ml of ethyl acetate, quenched with aqueous 1 M NaHC ⁇ 3, decolourised with 2.0g activated charcoal, and filtered. Ethyl acetate was then removed by vacuum distillation.
  • acetylated raffinose laurate obtained above was added to CF3COOH:H2 ⁇ (7:3) to form 20 - 50% w/v solution and agitated for a duration of time between 1 5 minutes to 2 hours, at room temperature (22 - 33 degree C).
  • the solvent was distilled off under reduced pressure.
  • the product is separated into carbohydrate fatty acid esters of varying degree of deacylation and or substitution by staged cooling between the temperatures of 10 and - 1 5 degree C.

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  • Saccharide Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP02733770A 2002-06-27 2002-06-27 Trans-acidolysis process for the preparation of surface-active carbohydrate fatty-acid esters Withdrawn EP1515980A1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SG2002/000133 WO2004002997A1 (en) 2001-02-24 2002-06-27 Trans-acidolysis process for the preparation of surface-active carbohydrate fatty-acid esters

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EP1515980A1 true EP1515980A1 (en) 2005-03-23

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EP (1) EP1515980A1 (ja)
JP (1) JP4580234B2 (ja)
AU (1) AU2002305964A1 (ja)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE227137C (ja) *
AT333781B (de) * 1972-11-06 1976-12-10 Krems Chemie Gmbh Verfahren zur herstellung neuer gemischter partialester
FR2503167A1 (fr) * 1981-04-06 1982-10-08 Blohorn Sa Procede de fabrication d'esthers de sucre et notamment de saccharose
US5424420A (en) * 1993-10-05 1995-06-13 Kraft Foods, Inc. Method for preparing saccharide polyesters by transesterification
US5440027A (en) * 1993-10-05 1995-08-08 Kraft General Foods, Inc. Method for preparing saccharide fatty acid polyesters by transesterification

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2004002997A1 *

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Publication number Publication date
JP2005538970A (ja) 2005-12-22
AU2002305964A1 (en) 2004-01-19
JP4580234B2 (ja) 2010-11-10

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