Title of Invention

NOVEL SURFACE ACTIVE AGENT OF A CLASS OF SUGAR FATTY ACID ESTERS AND METHOD OF PREPARATION

Abstract The invention concerns the field of surface active agent, in particular a novel surface active agent in the class of sugar fatty acid esters in solid, semisolid or liquid form, suitable to use in edible, pharmaceutical, agrochemical products. The invention also concerns a method for preparing said inventive novel surface active agent in the class of sugar fatty acid esters, produced in a single step process, comprising the step of reacting sugar, fatty acids and bifunctional acidic epoxide in the presence of a solvent, a catalyst (without using water, esters of fatty acids and fatty acyl chlorides).
Full Text FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
And
THE PATENTS RULES, 2003
COMPLETE SPECIFICATION
(See Section 10; rule 13)
"Novel surface active agent and method of preparation"
Prof. (Dr) Manohar. R. Sawant and Vishal. Y. Joshi having office at Department of Chemistry, Institute of Chemical Technology(Autonomous), Nathalal Paarikh Marg, Matunga (East), Mumbai- 400 019, State of Maharastra, India, an Indian Institute.
The following specification particularly describes the invention and the manner in which it is to be performed:
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Field of Invention
The present invention relates the novel surface active agents, and more specifically to the production of surface active agents in a class of sugar fatty acid esters in solid, semi solid or liquid form. The present invention more specifically relates to a novel product and a process for the production of novel surface active agent in a class of sugar fatty acid esters.
Back ground of Invention
In the world, the most abundant pure organic chemical in class of sugar is sucrose. Sucrose produced from sugar cane and sugar beets is ubiquitous in its availability and is of relatively low cost, only a fraction of a percent by weight is consumed as a chemical feed stock. The potential value of sucrose as a raw material has been recognized for many years and been the subject of considerable research. Sucrose is a particularly appropriate material for use in the formation of esterified products produced currently from petroleum-based materials because:
(a) it is a naturally occurring, relatively abundant renewable material,
(b) it is polyfunctional with three reactive primary alcohols that can readily be derivatized,
(c) it is non reducing sugar and thus does not have the potential for the wide variety of side-reactions in comparison to reducing sugars,
(d) it has a relatively easily hydrolyzed glycosidic linkage that allow sucrose polymers to be potentially more biodegradable than polymers made with other carbohydrates,
(e) it is a naturally occurring sweet carbohydrate in common use and therefore potentially useful in the formation of potential non-absorbable non caloric sweeteners,
Surfactants, the "natural" alternatives to surface active agents, are used in formulation of detergents, drugs, cosmetics, toiletries, agrochemicals and foods. The soaps (sodium and potassium salts of fatty acids) were replaced by the petroleum-derived surfactants. The interest aroused to develop surfactant based on esters of sugar and fatty acids.
A lot of work on various methods for synthesizing and purifying sucrose fatty esters has been done. There are only a few commercial source of these materials that meet the food and drug administration requirements, one being Royoto Sugar Esters made by the Mitsubishi-Kasai Food Company. The history of the sucrose esters, and their specifications, are discussed in the Royoto Sugar Ester Technical Information
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Bulletin and refer back to the work originally sponsored by the Sugar Research Foundation in 1954.
In sucrose there are eight positions where the formations of esters are formed when sucrose and fatty acids are reacted. Typically mono-esters, di-esters and tri-esters are formed with small amount of higher esters. When the reaction is with single fatty acid, (e.g. steraric acid, lauric acid) the analysis, by thin layer chromatography and liquid chromatography, shows that there are many different esters formed, typically 2-4 monoesters and up to 6-8 di-esters. When a commercial fatty acid mixture is used, the number of isomers is even higher. Each of the fractions has slightly different properties. For example, the lauric acid esters are liquid at room temperature while the stearic acid esters are solid, other products and/ or mixture gives semi solid products. They have different solubility in water as well as in organic solvents, but for the most part, as with most surfactants, the longer chain length esters, for example, sucrose stearates, are very insoluble in water than low chain alcohols. Although desirable, these differences in solubility and physical properties make an integrated production facility a difficult goal.
In order for a sucrose ester manufacturing process to be commercially useful it must be able to produce esters, which meet the FDA requirements of mono, di and tri-esters, free sucrose content, acid value, ash content, ethyl acetate content, arsenic content, heavy metal content, lead content, methyl ethyl ketone content, methyl alcohol content, dimethyl sulfoxide content, isobutyl alcohol content.
The FDA requirement for these sucrose esters are as follows:
(a) at least 80%by weight mono-, di-, and tri-esters,
(b) less than 5% by weight free sucrose,
(c) has an acid value is less than 6,
(d) no more than 2% by weight ash,
(e) no more than 350 ppm ethy acetate,
(f) no more than 3 ppm arsenic,
(g) no more than 50 ppm heavy metals, (h) no more than 10 ppm lead,
(i) no more than 10 ppm methyl ethyl ketone,
(j) no more than 10 ppm methyl alcohol,
(k) no more than 2 ppm dimethyl sulfoxide.
(1) no more than 10 ppm isobutyl alcohol.
Although it is not stated specifically in the FDA requirements, the above requirements allow for a significant amount of starting products to be carried over in to the final product. For example, almost all of the previous techniques recommend the use of the methyl esters of the fatty acids to make the final sucrose ester by trans-esterification. This leaves behind methyl esters in significant quantities, for example, 0.25% by weight residual methyl ester means that methanol will be generated by ingestion of the methyl ester by hydrolysis in the stomach that exceeds the FDA
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standard of 10 ppm. The literature does not teach a commercial process to meet all of the FDA requirements.
There exist several worldwide patents related to the technology of sucrose ester synthesis and purification. Patent considered with the synthesis mainly may be classified in to two categories (1) Trans-esterification synthesis (2) Direct synthesis.
Patents concerned with the trans-esterification synthesis may be roughly classified in to five categories:
(1) According to U. S. Pat. No. 2,893,990, Sucrose esters were produced by trans-esterification from fatty acyl methyl esters to sucrose is base-catalyzed in anhydrous solvents.
(2) According to U. S. Pat. No.3, 644,333, sucrose ester were produced by "transparent emulsion technology" where trans-esterification is performed under base catalyzed from a fatty acyl methyl ester in a micro emulsion under conditions that remove the product methanol by vacuum distillation ("transparent emulsion technology").
(3) According to U. S. Pat. No. 4, 683,299, sucrose esters were produced by fatty acyl chlorides, which are used as acyl donors in anhydrous solvents.
(4) According to U. S. Pat. No. 4, 614,718, sucrose esters were produced by an esterification or trans-esterification which is enzyme-catalyzed in either aqueous or non-aqueous solution.
(5) According to U.S. Pat. No. 3,349,081 where sucrose esters were produced by trans-esterification of sucrose with natural triglycerides in dimethylformamide, followed by stripping off the reaction solvent and treating the residue with an aqueous/butanolic sodium chloride solution and evaporating the separated butanol layer dryness.
The most "classical" method for the preparation of esters of a non-reducing sugar and fatty acids comprises the trans-esterification, reported in J. Amer. Oil. Chem. Soc. Vol. 34, 1957, pages 185-188, of sucrose with the methyl ester of a fatty acid in a solvent such as dimethylformamide and dimethylsulfoxide, in which both the sugar and the methyl ester of the fatty acid dissolve. This trans-esterification reaction is carried out in the presence of potassium carbonate as a catalyst and at a temperature of 90°C and under considerably reduced pressure. The limitation of this method is that the solvent is used is also toxic and requires to be completely removed before the use of the product, which in practice entails considerable problems.
To solve the problems associated with the use of the above mentioned solvents for both the sugar and the ester of fatty acids, a method is proposed in J. Amer. Oil. Chem. Soc, 1967, Vol.44, pages 307-309 for the preparation of a micro emulsion
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system of sucrose and the ester of a fatty acid in propylene glycol. In this case the sugar, in the presence of an emulsifying agent, usually a salt of a fatty acid, and the methyl ester of a fatty acid are dissolved in propylene glycol, after which the solvent is removed under considerably reduced pressure. In this method the main limitation is to obtain the reagents in a good micro emulsion with the desired particle size and, the removal of propylene glycol laboriously. Propylene glycol esters are also obtained as a by-product in this method.
A later modification of the solvent trans-esterification process in which water is used as the solvent is described in British Pat. No. 1,332,190. In this method the sugar is completely dissolved in the water in the presence of fatty acid soap, a fatty acid ester and a trans-esterification catalyst, after which the mixture is dehydrated under reduced pressure and at elevated temperature so that a homogeneous melt is obtained. This process also presents problems as regards the heating of the product containing water under reduced pressure, the pressure having to be carefully regulated as a function of the temperature to prevent hydrolysis of the fatty acid ester. For this reason this method is undesirably complicated for use on an industrial scale.
In addition, a solvent -free trans-esterification method is described in J. Amer. Oil. Chem. Soc. 1970, Vol. 47, pages 56-60. In this method sucrose is used in the molten state with the result that the method is carried out at a temperature of 170°C. After a short time, however, the sugar begins to degrade to a black tar-like mass with the result that the reaction with the fatty acid ester has of necessity to take place very rapidly. Normally the reaction is finished within 20 min. and sometimes even after only 2 min. The reaction should be carried out in the presence of an anhydrous soap free of alkali metal which serves to solubilise the fatty acid ester in the molten sugar and to catalyst the trans-esterification. Alkoxide, alkali and common soaps are completely unsuitable as a catalyst in view of the fact that their presence results in a very rapid decomposition of the sugar and brings about a black coloration of the mixture. In view of the problems relating to controlling the reaction since the reaction has to be completed very quickly on order to prevent degradation of the sugar, this reaction can only be carried out on a laboratory scale and offers little promise for application.
British patent Application No. 2,065,634 describes a method for the preparation of surface-active substances containing sugar esters in which solid granular sucrose, at least a triglyceride of fatty acid containing at least 8 carbon atoms and a basic trans-esterification catalyst are reacted at a temperature of 110°C-140°C under atmospheric pressure. However, the stating mixture should contain at least 10% by weight of fatty acid soap, while the optimum soap to an extent of at least 50%. The limitation of this method is that the end product is contaminated to a considerable extent with soap, in particular potassium soap.
While in direct synthesis sucrose and fatty acid ester reacts without using solvent (direct process). The reaction is usually carried out at temperature of from 110°C to 140°C under normal pressure. Direct process enjoys advantages in that no solvent is
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required and that the process under normal pressure but the problem here is how to mix the sucrose and the fatty acids ester, which are incompatible with each other. The problem has been solved by adding fatty acid soap to the reaction system or forming fatty acid soap in the reaction system. This further requires an additional procedure for separating and removing the fatty acid soap and purification of the final product.
The micro emulsion process and the direct process employ reaction temperatures between 110°C and 170°C. This requirement of reaction temperature is higher than that required in the solvent process (about 90°C). This results in considerable coloring of final products. The colored product requires an additional step of discoloring. Considering hydrophilic and lipophilic properties that are significant characteristics of sucrose fatty acid esters, it is difficult to obtain sucrose fatty acid esters having a broad range of HLB value, a measure for hydrophilic and lipophilc properties commonly adopted in the art by the micro emulsion process or the direct process on the other hand according to the solvent process, the products obtained are less colored as compared with those of the other processes owing to the relatively low reaction temperature and may have a broadened range of HLB value.
However since the both reactants and the catalyst form a uniform solution in the presence of a solvent, and necessary to add an acid to the reaction system for neutralization in order to stop the reaction rate and degree of ester replacement. More specifically, in the case of using for example, potassium carbonate as a catalyst, the reaction should be stopped by adding lactic acid, phosphoric acid or a solution containing the same or a combination thereof. To the reaction solution with out this neutralization step, the reaction would further proceed due to the presence of the catalyst having inter esterification activity even in the recovery and purification step of the product. This leads to reduction in yield of sucrose fatty acid esters having desired structure and composition. The neutralization step, in turn, brings about different problems that is water produced by neutralization should be removed by a dehydration step and the recovery and purification step become complicated because the reaction mixture contains a neutralization product e.g. potassium lactate in the case of neutralizing a potassium carbonate catalyst with lactic acid or a lactic acid solution.
According to JP-A-59-78200, discloses a process in which a mixture of a sucrose ester, a soap, and sucrose is melted by heating to obtain a sucrose ester having higher HLB value, i.e. a lower degree of substitution, than that of staring sucrose ester. The disclosure suggests starting with sucrose ester having an HLB value of 3 or more, preferably from 5 to 12. In the working examples of publication, a sucrose ester having an HLB value of 14.0 or 10.5 was prepared by starting with a sucrose ester having an HLB value of 10.5 or 7.0, respectively. No case has been reported in which a sucrose ester of low substitution is obtained from a sucrose ester of high substitution having an HLB value of less than 3.
The soap used as a reaction assistant in a solvent-free method generally has a large carbon atom number and is used in a large quantity. In the working example of JP-A-
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59-78200, for instance, a soap having 16 or 18 carbon atoms was used. However, since water solubility of soap decreases, easy purification techniques such as liquid-liquid extraction cannot be adopted without difficulty. With respect to the amount of soap, the publication states that the soap is preferably used in a relatively large amount, e.g. from 100 to 150% by weight based on the starting sucrose ester. The main limitation is in removing soap having a large carbon atom number; use of such a large quantity of soap also leads to economical and operational disadvantages in production on an industrial scale.
On the other hand, it has been proposed to replace the soap with a sucrose ester as a melting assistant to obtain a sucrose ester having high degree of substitution. JP-A-61-10589 discloses a process comprising reacting sucrose and fatty acid lower alkyl ester in a high temperature in the presence of a sucrose fatty acid ester having an average degree of substitution of 3 or more as a melting assistant. In the working example of the publication, sucrose, a sucrose stearate and a fatty acid lower alkyl ester were reacted at a high temperature of 160°C in the presence of potassium carbonate. However the resulting reaction mixture was brown tinted and found to contain a by produced long-chain soap.
While various techniques have been proposed for purifying the produced sucrose ester, none of them is satisfactory. For example, it has been suggested to treat the reaction product with a strongly alkaline aqueous solution followed by centrifugal separation to remove the soap thereby to control the alkali metal ion level below 1 ppm as disclosed in JP-A-1-207296 and JP-A-1-211594.
However any of these conventional processes have their own disadvantages and still leave room for further improvement. Summarizing it can be stated that the solutions presented in the prior art discussed above as regards the problems of obtaining a non-reducing sugar and fatty acid esters in a form such that the reaction can be carried out in an efficient manner are not effective.
Therefore there is needed to develop a method in which a non-reducing sugar, fatty acid, bifunctional acidic epoxide, solvent and a catalyst in single pot can be reacted at lower temperature to obtain a novel surface active agent in a class of sugar fatty acid esters with a high yield and less contaminants.
Objects of the invention:
It is an object of the present invention to provide a novel surface active agent.
It is another object of the invention is to provide a novel surface active agent in a class of sugar fatty acid esters.
It is further object of the invention is to provide a process for the production of surface active agents in a class of sugar fatty acid esters.
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It is yet another object of the invention is to provide surface active agents in a class of sugar fatty acid esters in solid, semi solid or liquid form.
It is another object of the present invention to a novel product and a process for the production of novel surface active agent in a class of sugar fatty acid esters.
It is yet another object of the present invention to a novel product and a process for the production of novel surface active agent in a class of sugar fatty acid esters by using sugar, solvent, catalyst, bifunctional acidic epoxide, fatty acid and/or other necessary ingredient.
It is other object of the invention is to provide a process for the production of novel surface active agent without using water and/or esters of fatty acids and/or fatty acyl chlorides.
It is another object of the invention is to provide a process for the production of novel surface active agent without using sugar in molten state and/or melting the necessary ingredients.
It is yet another object of the present invention is to manufacture the novel surface active agent in a single step synthesis.
It is other object of the present invention is to provide a novel surface active agent having ether as well as ester linkage between the head and tail portion of surface active agent.
It is another object of the invention is during manufacture of novel surface active agent, no trans-esterification process is performed.
It is yet another object of the invention is to provide a product and the process for the production of novel surface active agent which can be used on an industrial scale.
It is other object of the invention is to provide a process for the production of novel surface active agent at low temperature such that no sugar degradation occurs.
It is another object of the invention is to provide a process for the production of novel surface active agent without a black coloration of the mixture.
It is yet another object of the invention is to provide a process for the production of novel surface active agent using a non-reducing cyclic sugar having at least 6 carbon atoms and fatty acid, bifunctional acidic epoxide, solvent and a catalyst reacted with each other in a short time to obtain a product with a high yield and less contaminants.
It is yet another object of the invention is to provide a process for the production of novel surface active agent having a broad range of HLB value.
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It is yet another object of the invention is to provide a process for the production of novel surface active agent without using soap, and the soap having a large carbon atom number.
It is other object of the present invention to provide a process for the production of a novel surface active agent wherein the surface active agent is suitable to be used in edible, pharmaceutical and / or agrochemical formulations etc.
It is another object of the present invention to provide a process for the production of a novel surface active agent in batch or in continuous process.
It is other object of the present invention to provide a process for the production of a novel surface active agent by using a straight chain lower alcohol, preferably having one to four carbon atoms, most preferably having one carbon atom.
Statement of the invention:
A novel surface active agent in a class of sugar fatty acid esters of formula (I), as:

where in
Ri-0 is naturally occurring, non-reducing cyclic sugar (derived from sugar cane) having at least 6 carbon atoms,
R2is -CH2-
n is 1 or 2
R3 is saturated fatty acid ion of hydrocarbon straight chain having C7-C15 Carbon atoms;
is produced in a single step process by reacting sugar with fatty acids and bifunctional acidic epoxide in the presence of a solvent, a catalyst (without using water, esters of fatty acids and fatty acyl chlorides) wherein the content of monoester is from 50 to 95 % by weight, the content of diester is from 5 to 45 % by weight and the content of tri and higher polyester is from 0 to 5 % by weight in said sugar fatty acid esters. The process has the advantage of producing only small amounts of by-products (e.g, tri and higher polyester).
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A process for preparation of novel surface active agent in a class of sugar fatty acid ester comprises of,
a) adding a sucrose in to a vessel having an organic solvents;
b) dissolving sucrose at a very high speed stirring in the vessel;
c) passing an inert gas to the product obtained in the step (b);
d) Heating the mass of step (c), while stirring to a maximum temperature of 50°C;
e) cooling the saturated solution obtained in step (e) to temperature not below 20 °C;
f) adding a bifunctional epoxide and basic catalyst to the product of step (f);
g) refluxing the mixture of step (f), for at least 20 min at a temperature of above 50°C to initiate the condensation reaction;
h) continued the refluxing of mass of step (g) till the sucrose content is below
0.1%. i) cooling the reaction mass of step (h) while stirring to room temperature;
to obtain the invented novel surface active agent in a class of sucrose fatty
acid esters.
Detail description of the Invention.
A novel surface active agent in a class of sugar fatty acid esters of formula (I), as:

where in
Ri-0 is naturally occurring, non-reducing cyclic sugar (derived from sugar cane) having at least 6 carbon atoms,
R2is -CH2-
n is 1 or 2
R3 is saturated fatty acid ion of hydrocarbon straight chain having C7-C15 Carbon atoms;
is produced in a single step process by reacting sugar with fatty acids and bifunctional acidic epoxide in the presence of a solvent, a catalyst (without using water, esters of fatty acids and fatty acyl chlorides) wherein the content of monoester is from 50 to 95 % by weight, the content of diester is from 5 to 45 % by weight and the content of tri and higher polyester is from 0 to 5 % by weight in said sugar fatty acid esters. The process has the advantage of producing only small amounts of by-products (e.g, tri and higher polyester).
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The term "sugar" refers to a naturally occurring, non-reducing cyclic sugar (derived from sugar cane) having at least 6 carbon atoms preferably like glucose, sucrose, etc. preferably sucrose having following structure:
The term "surface active agent" refers to a substance, such as a detergent, added to a liquid to increase its spreading or wetting properties by reducing its surface tension.
The term "solid form" refers to a state of matter in which there is a three-dimensional regularity of structure, resulting the proximity of the component atoms, ions, or molecules and the strength of the forces between them. More precisely solid form has specific dimension.
The term "liquid form" refers to a phase of matter between that of a crystalline solid and compressed gas form. In a liquid the large-scale three-dimensional atomic (or ionic or molecular) regularity of the solid is absent. These bundles of ordered atoms, molecules, or ions move about in relation to reach other, enabling liquids to have almost fixed volumes, which adopt the shape of their containers.
The term "semi solid form" refers to a phase in between of solid and liquid phase.
The term "fatty acid" as referred herein is an organic compound consisting of a hydrocarbon chain and a terminal carboxyl group. Chains length ranges from one hydrogen atom (methanoic acid) to nearly 30 carbon atoms. These long-chain fatty acids generally have an even number of carbon atoms with saturated nature.
The term "sugar fatty acid esters" as referred herein is surface active agent in a class of natural surface active agents. It has sucrose as a hydrophilic group and fatty acid as hydrophobic group. These groups are connected to each other via ether as well as ester linkage.
The term "trans-esterification" as referred herein is the chemical process where a ester linkage is form first with lower alcohols preferably C1 to C4. Next lower esters are replaced by long chain alcohols preferably C10 to C30 under suitable catalytic conditions.
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The term "FDA" as referred herein is Food and Drug Administration.
The term "HLB" as referred to a hydrophilic lipophilic balance and gives the idea about functional group present on the surface active agent.
The term "non reducing sugar" as referred herein is a sugar that cannot donate electrons to other molecules and therefore cannot act as a reducing agent. Sucrose is the most common non reducing sugar. The linkage between the glucose and fructose unit in sucrose, which involves aldehyde and ketone groups, is responsible for the inability of sucrose to act as a reducing sugar.
The term "single pot synthesis" or "one pot synthesis" are used herein interchangeably and refers to one step and or one pot synthesis where more than three reactants reacts in single step to give desired product.
The term "head part" or "hydrophilic part" are used herein interchangeably and refers to a part of surface active agent which has an affinity for water.
The term "tail part" or "hydrophobic part" are used herein interchangeably and refers to a part of surface active agent which has lacking affinity for water.
The term "bifunctional acidic epoxide" or "halohydrocarbyloxiranes" are used herein interchangeably and refers to a compound having epoxide ring with two active functional groups at the two ends.
The term "alkali earth metal salts" or "alkaline catalyst" are used herein interchangeably and herein refers to inorganic salts of alkali metals like sodium, potassium such as oxides 1, carbonates, hydroxides, hydrogen carbonates and methoxide or organic base like alkyl amine, pyridine. Most preferable alkaline catalysts are sodium methoxide and sodium hydroxide.
The present invention is focused on single step synthesis of sucrose alkyl esters. It is accordingly one object of the present invention to provide a new group of ester and ether derivatives of sucrose. It is further object of the invention to provide a novel class of sucrose esters and ethers which are useful as food bulking agents, reduced calorie sweeteners, fat replacement agents for food products, stabilizing agents for food and beverage products, thickening and emulsifying agents for food products, adhesives and surface active agent in ethical pharmaceuticals. By the use of selected reaction conditions, the desired product may be obtained. By appropriate selection of the type of fatty acids different chemical as well as physical properties can be incorporated in to the resulting sucrose compound.
A still further object of the present invention is to provide a method for the preparation of a novel surface active agent based on sucrose alkyl ester, in good yields and with improved specificity over methods known to the prior art. Preferably,
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the objective of this invention is to provide a commercial process that overcomes the limitations of previous process with particular attention to providing an integrated production facility that has no waste streams and minimal air emissions. This is not a trivial point, since the processes, which are more economically viable, have always been plague by high waste streams of many solvents.
The present invention discloses reactions of bifunctional epoxide with sucrose and fatty acids. It acts as bridge between sucrose and fatty acid molecule. The novel surface active agent disclosed herein is also presented by the following formula.

where in
Ri-0 is naturally occurring, non-reducing cyclic sugar (derived from sugar cane) having at least 6 carbon atoms, preferably sucrose;
R2is -CH2-;
n is 1 or 2;
R3 is saturated fatty acid ion of hydrocarbon straight chain having C7-Q5 Carbon atoms;
It will be appreciated that the process of the present invention, like that of said patent, is completely different from the previous ones, in that it uses trans-esterification process with or with out solvent or direct process. Some of the advantages of present process over previous ones are,
(1) Present invention is single step synthesis (one pot synthesis) while previous process are more then one steps reaction. Additionally rate of reaction and overall conversion for sucrose monoesters are considerable than previous efforts. Present process can replace the trans-esterification process and direct process. The notable feature is single organic polar solvent is used through out sucrose ester manufacturing.
(2) The preferred organic solvent is lower straight chain alcohols and can be easily removed from the reaction mass with out affecting the quality of final product. Moreover it can complies all the FDA limitation mentioned previously.
(3) Previous researcher suggested that fatty acid cannot be used directly for esterification with sucrose so they moved towards ester of fatty acids and fatty acyl chlorides to optimize the esterification process. Ester of fatty acids and fatty acyl chlorides are very costly and can't be completely converted to product. So here we try to react fatty acid molecule slightly differently with sucrose molecule in single step and single solvent condition. We can say that the present invention
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is free form use of ester of fatty acids, fatty acyl chlorides for esterification process. Also costly and toxic solvents like dimethylfomamide, tetrahyrofuran, glacial acetic acid etc. replace by cheap and easily removable solvent.
(4) The catalyst used for the reaction is alkali metal's salts which are quite easily available and give almost clean reaction. Contaminating and un reacted material can be easily removed from the crude reaction product.
(5) The reaction temperature which is most key parameter for quality and appearance of final product (i.e. Sucrose ester). Comparatively low reaction temperature helping to control charring and degree of esterification effectively.
(6) Final product (i.e. Sucrose ester) can be available in various physical forms like solid, liquid, semisolid.
By the present invention it has been discovered that conducting the reaction of sucrose with bifunctional epoxide and fatty acids described herein enables one to obtain specificity of the reaction at the 6 positions of sucrose. The resulting products are novel sucrose condensation products where in sucrose molecules are linked with bifunctional epoxide by ether linkage. After condensation, resulting product is further reaction with fatty acid to afford ester linkages which may be linear and which in general represent a new class of sucrose products having wide variety of uses.
As especially novel feature of the invention concerns the method by which the sucrose products of the present invention are produced. According to the invention, it has been discovered that sucrose condensation products comprising sucrose molecule linked to the bifunctional acidic reactant are produced in high yields and purity by condensation reaction in single solvents. On further addition of fatty acid to pre-condensed product gives corresponding sucrose esters.
The process is conducted generally by dissolving the appropriate amount of sucrose in a organic solvent and then slowly add bifunctional epoxide, base catalyst and fatty acids in it. The prior drawbacks have now been overcome and in accordance with the present invention sugar esters are synthesized in a substantially anhydrous organic liquid solvent system in the presence of a bifunctional epoxide to produce non-toxic edible sugar esters particularly adapted for use in food products.
The "sucrose" used in the process of the inventions is normally in the form of particulate refined sugar such as granular sugar. The sugar particle size is not critical but particle which are too large can be difficult to disperse adequately in the reaction mixture and it is there for generally preferred to use sucrose of particle size smaller than 250 microns to expedite synthesis and to provide a high yield of sugar esters. One of the unique features of the present invention is that methyl esters of fatty acids or organic acid chloride or alkyl acyl chloride are not required for the reaction. The sugar and fatty acid are coupled via bridge called bifunctional epoxide in single step reaction.
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The reaction medium is straight chain lower alcohol from Q to C4, preferably solvent are C\ and C2 alcohols while most preferably solvent is C\ alcohol.
The preferable "bifunctional epoxide" is from halohydrocarbyloxirane such as epichlorohydrine. One end of bifunctional epoxide is reacted selectively at 6 position of sucrose and second end is reacted with fatty acid to effort sucrose esters in single step with organic liquid solvent.
Possible "fatty acids" for carrying out the process according to the invention are straight chain, saturated fatty acids having a chain length of 8 to 16 carbon atoms in the fatty acid radical. One preferred method of the practicing the present invention involved the step of adding a size reduced sugar powder to liquid solvent such as lower straight chain alcohols ranges between C1 to C4. This step is best carried out by employing vigorous agitation and gentle heat such as about 50°C and above to aid in dissolving as much sugar as possible in the solvent with out burning or charring. It is important that virtually no water be present in the system and for best results an anhydrous liquid system is employed. In order to provide an hydrous system a dry gas pure is preferably employed to strip moisture from the liquid reaction system while the sugar is being crushing, added and then after during reaction. An inert gas preferably nitrogen purge is used to advantage for stripping water from the system.
The "alkaline catalysts" suitable for the process of the invention includes various inorganic salts such as oxides, carbonates, hydroxides, hydrogen carbonates and methoxide or organic base like alkyl amine, pyridine. Most preferable alkaline catalysts are sodium methoxide and sodium hydroxide. In the sense of the present invention, the presence of less than 5% by weight of the catalyst based on the weight of the reaction mixture is particularly preferred. The one pot condensation of sugar, bifunctional epoxide and fatty acid are preferably carried out at a temperature in the range from 50 to 80°C in particular at 55 to 75°C at atmospheric pressure in the course of 0.5 to 4 hours. In this case, an equimolar ratio of fatty acid, bifunctional epoxide and sucrose can be set. It is however preferred to employ an excess of bifunctional epoxide to sucrose during condensation. More over the preferred ratio of fatty acid to condensed product of sucrose is in the range of 0.8 to 1 mol of fatty acid to 1 mol of sucrose condensed product.
The proposed process according to the invention is carried out in round bottom three neck flask. Over head stirrer with 600 to 4000 rpm is employed and Teflon paddle is used for agitation. The Teflon paddle is placed above but very close to the bottom of the flask. The preferable height is 2 mm from the flat bottom. While width of the paddle is 5 cm. The influence of external mass-transfer resistance was studied for the transfer of the limiting reactant to the external surface of the catalyst. The effect of speed of agitation was studied at 600, 800, 1000, 1200 and 1500 rpm and it was found that the conversion and product distribution was practically similar in all the cases. Thus the external resistance to mass-transfer was absent beyond 600 rpm. However to be on safer side further experiments were conducted at 800 rpm.
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To carry out the process according to the invention, the individual components are weighed in. Fine powder of sucrose was kept in vacuum desiccators to avoid moisture contamination and than charge in to the three necks round bottom flask along with organic alcoholic solvent. Initially stir the reaction mass at very high speed and gentle heat such as about 50°C and above to aid in dissolving as much as possible in solvent with out burning or charring. Cool the reaction mass up to the 20°C and then add previously weighted bifunctional epoxide and basic catalyst in to the reaction mass with fatty acid dissolve in same organic solvent as taken for the reaction media.
After it, slowly raise the temperature to reflux temperature of the solvent. The preferred reaction time is 0.5 to 4 hr. for the reaction, in which almost all the sucrose, bifunctional epoxide and fatty acid were condensed. The reaction is maintained at a constant temperature between the optimum range of 55° to 70°C and agitation speed is 800 rpm. During the bifunctional epoxide and fatty acid addition the nitrogen purge is also preferable to maintain an anhydrous reaction system. Care should be taken to avoid burning and charring of the selected sugar since such degradation will impair the quality of the sugar ester and materially reduce yields and make it extremely difficult or virtually impossible to separate the desired sugar ester from the reaction mass for subsequent refinement for use as a food product ingredient. According to the U. S. Pat. No -6,281,351, the addition of the bifunctional epoxide to the reaction mass should perform about 55°C because lower temperature from about 30°C to 40°C may produce polymeric product of sucrose-epoxide-sucrose.
The reaction is continuously monitored by thin layer chromatography (TLC). The TLC migration of the final product is different from sucrose which confirms that spacer is properly connected between sucrose and fatty acid. According to U. S. Pat. No -6,281,351 if sucrose and spacer are reacted and no further condensation with fatty acid than TLC migration spot of condensed product and sucrose remains same. In present case we get different spot than sucrose migration so it proves fatty acid is attached to the condensed product form from sucrose and bifunctional epoxide. Also small amount of sample when dissolve in the water and shake well generate sufficient amount of foam which indicates sucrose ester is form which have surface active properties.
After completing the reaction the reaction mass is cool up to room temperature. During the cooling stirring is continuing. There is no need for neutralization. As the pH of the mass is in between 7.1 to 8.2 and to prevent the reversible reaction if needed the pH is to be maintain between 7 to 8.5 by using acid for example hydrochloric acid, sulfuric acid etc. Suitable acid to maintain the pH 7 to 8.5 is hydrochloric acid. No special conditions are chosen to distill of the organic solvent from the reaction mass. In present invention methanol (b.p. 65°C) is used as best reaction media which is distilled out by rotary evaporator to get viscous mass at the end. Apply the high vacuum at the end to remove all the solvent traces from the reaction mass by regulate the rotary evaporator's temperature at range of 50°C to
16

65°C. The bifunctional epoxide has boiling point more than 117°C and un-reacted can removed with traces of reaction solvent.
The viscous product of the proposed process contains the sucrose mono-ester, sucrose higher esters, un reacted fatty acid, bifunctional epoxide and bye products. In bye product sucrose-epoxide condensate which will removed by solvent extraction. After the distillation of solvent nearly 30 to 50 % weight by weight water is added in the reaction mass and stir the mass for 20 to 30 min to get hazy solution. The collected liquid is washed with ethyl acetate which removes un-reacted fatty acid residual. After repeated the solvent extraction steps, the liquid stream of ethyl acetate with un-reacted fatty acid is collected and distilled the ethyl acetate to recover it by leaving the fatty acid as residue.
Repeat above process twice to ensure that all the un-reacted fatty acid is separated from the aqueous phase. Dilute the final mass with more amount of water to get the transparent mass and stir it for 20min.When the aqueous solution is treated under the above-mentioned conditions the concentrated liquid usually has a water content of 60 to 90% by weight and solid content of 40 to 4% by weight. The treated liquid which is in the form of solution or slurry may be further concentrated to higher solid concentration by other methods e.g. evaporation under reduced pressure. However it should be avoided to concentrate to such an extent as making spray drying in the next step difficult.
The concentrated liquid containing 60 to 90% by weight of water which is in the state of a sort of slurry is then dehydrated and dried. The present inventors have found that spray drying is particularly suitable for dehydration and drying of the sucrose ester slurry. The dehydration and drying may be conducted by other know methods or devices, e.g. a conventional vacuum dryer such as a channel agitated dryer. However these means are disadvantageous for example it is known from Japanese patent publication kokoku No. 37-9966 that the dehydration and drying of an aqueous solution and is obliged to conduct at a high temperature for a long time and consequently it causes undesirable phenomena such as rise of acid value resulting from decomposition of sucrose ester, marked coloration and caramel formation. Also in case of flash dryer where in a slurry is continuously heated, fed to a vacuum chamber and released, difficulty is encountered. When a sufficient drying is desired because of large latent heat of water (over 500 Kcal / Kg). Even if these difficulties are over come the sucrose ester dehydrated and dried under vacuum is in the molten state and therefore, it requires a pulverization step after taking out of the drier and cooling to less than the melting point to solidify, for instance, by blowing a cold air.
As dehydration and drying of slurry under vacuum gives us semisolid, liquid and solid form of surface active agent in a class of sugar fatty acid ester. Withdrawal of the molten sucrose ester from a drier under vacuum gives us semisolid and solid form. Cooling for solidification of the semi solid mass to get the surface active agent in a class of sugar fatty acid ester in form of solid. Pulverization of the solidified
17

sucrose ester from solid form to get product in a form in which the particle size is below 0.1mm.
It is not desirable from the economical point of view and more over accompanies a risk of dust explosion in the pulverization step.
The dehydration and drying means for sucrose ester slurry by the spray drying involve in the present invention can eliminate the defects of the above mentioned drying means. In the present invention the slurry is continually fed to spray drying tower by a pump and dispersed in the form of mist through a rotary disk or a nozzle, preferably through the letter since the surface area of water evaporation is made extremely large by spray drying, dehydration and drying can be completed in several seconds after spraying. The slurry fed to the spray drying tower is kept at a temperature of 200°C to 250°C, preferably 200°C to 220°C in consideration of quality. By maintaining above inlet temperature the out let temperature id observed at 80 to 93°C. The hot air passed through the tower should have a heat energy sufficient to evaporate water included in the slurry, and accordingly when the temperature of the air is low, a large quantity of air is required as a matter of course. The humidity of the air passed is also important as well as the temperature and it is economical that the absolute humidity of the air is from 0.01 to 0.04 Kg water/Kg dry air.
The parameter such as volume, diameter and height of the spray drying tower is determined on the basis of the above mentioned spray drying conditions. Powder of the sucrose fatty acid ester having a water content of not more than 7% by weight can be continuously taken out from the lower part of the tower. Like this, according to the present invention, a powder of purified sucrose fatty acid esters can be economically produced from the crude reaction mixture obtained by the one step condensation of sucrose, bifunctional epoxide and fatty acid.
The product obtained in the invented process is:
a) maintaining the pH, if necessary between 7.0 to 8.5 to prevent the reversible reaction;
b) distilling out the unreacted bifunctional acidic epoxide and reaction solvent to get a viscous mass to obtain the novel surface active agent in a class of sucrose fatty acid ester in semi solid form;
c) adding water in the product obtained in step (b);
d) stirring the product obtained in step (c) for at least 10 minutes to get hazy solution;
e) washing the solution of step (d) with ethyl acetate to remove unreacted fatty acid and sucrose epoxide to obtained the novel surface active agent in a class of sucrose fatty acid ester in liquid form;
f) diluting the product, obtained in step (e) with water to get a transparent pump able mass of sucrose fatty ester slurry;
g) stirring the mass obtained in step (f) for at least 1 minutes;
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h) spray drying the mass obtained in step (g) to obtained the novel surface active agent in a class of sucrose fatty acid ester in solid/powder form.
The present invention is more specifically described and explained by means of the following examples. It is to be understood that the present invention is not limited to these examples.
Example-1
A novel surface active agent in class of sucrose fatty acid ester was prepared by reacting the following materials:
Sucrose 50.00g (0.1461 mol); Epichlorohydrine 13.5 g (0.1459 mol); Dodecanioc acid ( Capric acid) 21.9 g (0.1095 mol); Methanol 219 ml; Sodium methoxide 9 g ; Ethyl acetate 150 ml ; Water 100 ml; 50.0g (0.1461 mol) of sucrose (having a particle size of less than 250 microns) was introduced in to a 500 ml three-necked round bottom flask equipped with a stirrer; reflux condenser and dropping funnel under nitrogen environment. Add 170 ml methanol in it and the suspension was kept mixed by means of a 5 cm diameter inclined paddle, which was rotated by an electric motor at between 600 and 4000 rpm, depending on the viscosity of the mixture and requirement. The further specification of reaction vessel up to 3 liter is shown in the table.

No. Capacity (ml) Width of paddle (cm) Height of paddle from bottom (mm) Optimizedagitation speed(rpm)
1 250 2.14 3.0 800
2. 1000 3.5 3.0 800
3. 3000 5.0 3.0 800
Initially high speed mixing is beneficial for solubilization of sucrose particle in to the methanol, so agitation was set between 1000-1200 rpm. Dissolve 21.9 g (0.1095 mol) dodecanoic acid, 9g sodium methoxide and 13.5g (0.1459 mol) epichlorohydrine in 40 ml methanol. Add the mixture in reactor using doping funnel and stir the reaction mass for 15 min properly at 1200 rpm and then slow down the rpm speed to 800 rpm with start heating the reactor. The temperature was set between 55° to 60°C for approximately 0.5 to 4 hr to complete the reaction. An aliquot of the reaction was removed for thin layer chromatography (TLC) analysis. The reaction mixture aliquot was extracted with an equal volume of ethanol-chloroform (1:1) and spotted on silica plates developed in hexane: ethanol: ether: acetic acid (60:20:20:1) plates were sprayed with a 0.5% bromothymol blue solution prepared in ethanol and 5 ml sulfuric acid and dry at 100°C to visualize carbohydrate compound. This method allowed
19

visualization of the extent of reaction and approximation of yield by comparison with standard sucrose solution. TLC of the crude esters showed a range of substituted esters, with the spots of lower Rf corresponding to the less substituted sucrose esters, and the spots of higher Rf corresponding to higher substituted sucrose esters. Comparison of the TLC result of the reaction aliquot with that of the sucrose showed almost complete conversion to the sucrose monoesters and sucrose di esters with small increase in the amount of free fatty acid.
Example-2
The product obtained from example-1, was taken for distillation without adjusting the pH of the mass. Remove the entire methanol and unreacted acidic epoxide by applying vacuum in rotary evaporator and temperature kept below 45°C. Ensure the entire methanol and unreacted acidic epoxide was distilled out to get the novel surface active agent in a class of sucrose fatty acid ester in semi solid form. The yield of mixed sucrose ester in semi solid form was 58.56 g (66%) by weight of the theoretical stoichiometric yield of sucrose
Example-3
The product obtained from example-2, was taken in a vessel and 50 ml of water is added in the product and stir for 10 min at 800 rpm. Filter the reaction mass on celite to remove un-reacted sucrose epoxide and fatty acid. Collect the filtrate and add 75 ml ethyl acetate in it and take both the layer in separating funnel for layer separation. Collect aqueous layer from the funnel and repeat the extraction twice with ethyl acetate with same amount. Collect the aqueous layer to obtained get the novel surface active agent in a class of sucrose fatty acid ester in liquid form. The yield of mixed sucrose ester in liquid form was 65.56g (75%) by weight of the theoretical stoichiometric yield of sucrose
Example-4
The product obtained from example-3, was concentrate to get viscous mass by applying high vacuum below 45°C. After getting the viscous mass again dilute it with 50 ml of water and is spray drying. The yield of mixed sucrose ester in solution form was and spray dried was 55.37g (63%) by weight of the theoretical stoichiometric yield of sucrose.
ExampIe-5.
The surfactant was prepared by same procedure as mentioned in example-1 except for changing the fatty acid to myristic acid. Present example use myristic acid (24.96g, 0.1095 mol) as hydrophobic tail. To get semisolid form of novel surface active agent in class of sucrose fatty acid ester, processed as example-2. The yield of mixed sucrose ester in semi solid form was 65.5g (71%) by weight of the theoretical stoichiometric yield of sucrose
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Example-6.
To get liquid form of novel surface active agent in class of sucrose fatty acid ester, processed as example-3. The yield of mixed sucrose ester in solution form was 67.02g (73 %).
Example-7.
To get solid form of novel surface active agent in class of sucrose fatty acid ester, processed as example-4. The yield of mixed sucrose ester in solid form was 56.92g (62%) by weight of the theoretical stoichiometric yield of sucrose.
Example-8.
The surfactant was prepared by same procedure as mentioned in example-5 to 7 except for changing the fatty acid to palmitic acid. Present example use palmitic acid (28.03g, 0.1095 mol) and the yield of mixed sucrose ester in semi solid form was 63.21g (65%), in solution form was 68.08g (71%) and spray dried was 59.45g (62%) by weight of the theoretical stoichiometric yield of sucrose.
Example-9.
The surfactant was prepared by same procedure as mentioned in example-8 except for changing the fatty acid to decanoic acid. Present example use decanoic acid or capric acid (18.83g, 0.1095 mol) and the yield of mixed sucrose ester in semi solid form was 63g (75%) in solution form was 65.19g (78%) and spray dried was 54.92g (65%) by weight of the theoretical stoichiometric yield of sucrose.
Example-10.
The surfactant was prepared by same procedure as mentioned in example-9 except for changing the fatty acid to octanoic acid. Present example use octanoic acid or caprylic acid (15.76g, 0.1095 mol) and the yield of mixed sucrose ester in semi solid form was 60.2 lg (75%) in solution form was 62.78g (79%) and spray dried was 51.92g (65%) by weight of the theoretical stoichiometric yield of sucrose.
Example-11.
The surfactant was prepared by same procedure as mentioned in example-1 to 4 except for changing the catalyst to Sodium hydroxide. Present example use sodium hydroxide instead of sodium methoxide in same quantity and the yield of mixed sucrose ester was in semi solid form was 55.2g (62%) solution form was 63.02g (72%) and spray dried was 53.12g (60%) by weight of the theoretical stoichiometric yield of sucrose.
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Example-12.
The surfactant was prepared by same procedure as mentioned in example-5 to 7 except for changing the catalyst to Sodium hydroxide. Present example use Sodium hydroxide instead of sodium methoxide in same quantity and the yield of mixed sucrose ester in semi solid form was 56g (61%), in solution form was 65.18g (71%) and spray dried was 53.Og (57.72%) by weight of the theoretical stoichiometric yield of sucrose.
Example-13.
The surfactant was prepared by same procedure as mentioned in example-8 except for changing the catalyst used. Present example use Sodium hydroxide instead of sodium methoxide in same quantity and the yield of mixed sucrose ester in semi solid form was 60.g (62%), in solution form was 65.20g (68%) and spray dried was 56.57g (59%) by weight of the theoretical stoichiometric yield of sucrose.
Example-14.
The surfactant was prepared by same procedure as mentioned in example-9 except for changing the catalyst used. Present example use Sodium hydroxide instead of sodium methoxide in same quantity and the yield of mixed sucrose ester in semi solid form was 53.lg (63%), in solution form was 62.67g (75%) and spray dried was 51.81g (62%) by weight of the theoretical stoichiometric yield of sucrose.
Example-15.
The surfactant was prepared by same procedure as mentioned in example-10 except for changing the catalyst used. Present example use Sodium hydroxide instead of sodium methoxide insame quantity and the yield of mixed sucrose ester in semi solid form was 55.47g (69%), in solution form was 59.60g (75%) and spray dried was 49.27g (62%) by weight of the theoretical stoichiometric yield of sucrose.
Example-16.
The surfactant was prepared by same procedure as mentioned in example-1 to 15 except for changing the temperature of the reaction. Present example operated at the temperature range of 65 to 70°C. The over all conversion and reaction rate were not so much affected at elevated temperature. The major problem at higher temperature was charring of sugar/sucrose, and colour of the final quality was slightly darker in appearance than lower temperature product. The yield was almost same in higher and lower temperature reaction condition.
22

Example-17.
The surfactant was prepared by same procedure as mentioned in example-1 to 4 except for changing the reaction solvent. Present example use ethanol as reaction solvent in same quantity. The major disadvantage to use ethanol as a solvent was conversion was lower down in comparison of methanol. The solubility of sugar was maximum in methanol while compare with ethanol and the yield of mixed sucrose ester in semi solid form was 51.58g (59%), in solution form was 57.69g (66%) and spray dried was 50.37g (58%) by weight of the theoretical stoichiometric yield of sucrose. As decrease in over all conversion further optimization was done with methanol as a reaction solvent.
Example-18.
The surfactant was prepared by same procedure as mentioned in example-17 except for changing the reaction solvent. Present example use 1 -propanol as reaction solvent in same quantity. The major disadvantage to use 1-propanol as a solvent was conversion was lower down in comparison of ethanol and methanol. The solubility of sugar was maximum in methanol, ethanol and 1-propanol respectively. While compare with 1-propanolthe yield of mixed sucrose ester in semi solid form was 50g (57%), in solution form was 55.07g (63%) and spray dried was 48.37g (55%) by weight of the theoretical stoichiometric yield of sucrose. As decrease in over all conversion further optimization was done with methanol as a reaction solvent.
Example-19.
The surfactant was prepared by same procedure as mentioned in example-18 except for changing the reaction solvent. Present example use 1-butanol as reaction solvent in same quantity. The major disadvantage to use 1-butanol as a solvent was conversion was lower down in comparison of methanol and ethanol while more than 1-propanol. The solubility of sugar was maximum in methanol, ethanol, 1-butanol and 1-propanol respectively While compare with 1-butanol the yield of mixed sucrose ester in semi solid form was 51.23g (58%), in solution form was 56.82g (65%) and spray dried was 50.70g (58%) by weight of the theoretical stoichiometric yield of sucrose. As decrease in over all conversion further optimization was done with methanol as a reaction solvent.
Example-20.
From the above examples a diluted aqueous sucrose ester solution can be prepared as desired and later it was taken for drying using spray dryer. The aqueous slurry was fed to a spray drying tower quipped with nozzle spray. The conditions of spray drying were as follows:
Evaporation rate of water at 250°C inlet temperature = approximately 1000ml/hr. Maximum air inlet Temperature = 250°C
23

Heater capacity =1.5 Kw
Feed pump flow rate = 0 to 1250 ml/hr
Spray system = 0.5 mm jets
Spray/ Hot air flow = co current
Dimensions = 1200 X 500 X 600 mm (height x width x depth)
Fed air = 30 to 110Nm3/hr
Temperature of air at inlet = 90 to 100°C
Temperature of air at outlet = 210 to 230°C
The powder sucrose ester obtained from the lower part of the spray drying tower is
light colored (white to off-white), the water content found in the spray dried product
is found to be less than 0.5% by weight and the product has good flow ability. The
ester content of obtained sucrose ester powder was same as it was before drying thus
there was no change in ester content occurred during spray drying.
References:
1. Kirk-Othmer, encyclopedia of Chemical technology, 3 rd Edition, volume 21, John Wiley & Sons, New York, Page 921-948 (1983).
2. J. Amer. Oil. Chem. Soc. Vol. 34, 1957, pages 185-188
3. Royoto Sugar Ester Technical Information Bulletin sponsored by the Sugar Research Foundation in 1954.
4. U. S. Pat. No. 2,893,990
5. U. S. Pat. No.3,644,333
6. U. S. Pat. No. 4,683,299
7. U.S. Pat. No. 3,349,081
8. U.S. Pat. No. 4, 614,718
9. J. Amer. Oil. Chem. Soc. Vol. 34,1957, pages 185-188.

10. J. Amer. Oil. Chem. Soc, 1967, Vol.44, pages 307-309.
11. British Pat. No.1,332,190.
12. J. Amer. Oil. Chem. Soc. 1970, Vol. 47, pages 56-60.
13. British patent Application No. 2,065,634.
14. JP-A-59-78200. 15.JP-A-61-10589

16. JP-A-1-207296
17. JP-A-1-211594
18. .U. S.Pat. No-6,281,351
19. Japanese patent publication kokoku No. 37-9966
24

We claims:
1. A novel surface active agent in a class of sugar fatty acid esters of formula (I), as:


where in
Ri-0 is naturally occurring, non-reducing cyclic sugar (derived from sugar cane) having at least 6 carbon atoms,
R2is -CH2-
n is 1 or 2
R3 is saturated fatty acid ion of hydrocarbon straight chain having C7-C15 Carbon atoms;
is produced in a single step process by reacting sugar with fatty acids and bifunctional acidic epoxide in the presence of a solvent, a catalyst (without using water, esters of fatty acids and fatty acyl chlorides) wherein the content of monoester of novel surface active agent is from 50 to 95 % by weight, the content of diester is from 5 to 45 % by weight and the content of tri and higher polyester is from 0 to 5 % by weight in said sugar fatty acid esters. The process has the advantage of producing only small amounts of by-products (e.g., tri and higher polyester).
2. A novel surface active agent as claimed in claimed 1, where the sugar selects from naturally occurring non reducing cyclic sugar derived from sugarcane having at least 6 carbons preferably glucose, sucrose and others, most preferably is sucrose.
3. A novel surface active agent as claimed in claimed 1, wherein the fatty acid is straight chain, saturated fatty acids having a chain length of Cg to Ci6 carbon atoms preferably C7 to Q5.
4. A novel surface active agent as claimed in claim 1, wherein the bifunctional acidic epoxide is selected from halohydrocarbyloxiranes with following chemical formula

where n=l or 2, R is -CH2- group and X is functionally reactive group such as a halogen. Most preferentially halohydrocarbyloxiranes is ephichlorohydrine.
25

5. A novel surface active agent as claimed in claim 1, wherein the solvent is selected from a straight chain lower alcohol from C1 to C4 preferably solvent are C1 and C2 alcohol while most preferably solvent is C1 alcohol.
6. A novel surface active agent as claimed in claim 1, wherein catalyst is selected from the group consisting of alkali metal hydroxides and methoxides and is used in a strength of not more than 5% weight by weight of the total reaction mixture.
7. A novel surface active agent in a class of sugar fatty acid esters as claimed in claim 1 to 6, wherein novel surface active agent is in the form solid, semi-solid or liquid form, suitable to use in edible, pharmaceutical, agrochemical products.
8. A process for preparation of novel surface active agent, as claim in above claims, in a class of sugar fatty acid ester comprises of,

a) adding a sucrose in to a vessel having an organic solvents;
b) dissolving sucrose at a very high speed stirring in the vessel;
c) passing an inert gas to the product obtained in the step (b);
d) heating the mass of step (c), while stirring to a maximum temperature of 50°C;
e) cooling the saturated solution obtained in step (e) to temperature not below 20 °C;

f) adding a bifunctional epoxide and basic catalyst to the product of step (f);
g) refluxing the mixture of step (f), for at least 20 min at a temperature of above 50°C to initiate the condensation reaction;
h) continued the refluxing of mass of step (g) till the sucrose content is below
0.1%; i) cooling the reaction mass of step (h) while stirring to room temperature;
to obtain the invented novel surface active agent in a class of sucrose fatty
acid esters .
9. A process as claimed in claim 8, wherein the obtained novel surface active agent
is converted into a semi-solid form by following the steps of:
j) maintaining the pH, if necessary between 7.0 to 8.5 to prevent the reversible
reaction; k) distilling out the unreacted bifunctional acidic epoxide and reaction solvent;
to get a viscous mass to obtain the novel surface active agent in a class of sucrose fatty acid ester in semi solid form.
10. A process as claimed in claim 9, wherein the obtained semi-solid form is further
processed as follows:
1) adding water in the product obtained in step (k)
m) stirring the product obtained in step (1) for at least 10 minutes to get hazy solution;
26

n) washing the solution of step (m) with ethyl acetate to remove unreacted fatty acid and sucrose epoxide;
to obtained the novel surface active agent in a class of sucrose fatty acid ester in liquid form.
11. A process as claimed in claim 10, wherein the obtained liquid form is further
processed as follows:
o) diluting the product, obtained in step (n) with water to get a transparent pump
able mass of sucrose fatty ester slurry; p) stirring the mass obtained in step (o) for at least 1.0 minutes; q) spray drying the mass obtained in step (p);
to obtained the novel surface active agent in a class of sucrose fatty acid ester in solid/powder form.
12. A novel surface active agent in a class of sugar fatty acid ester and a process for
its preparation as herein describes and exemplified.
Dated this on25day of July, 2006.
(Prof. (Dr) Manohar. R. Sawant)
Department of Chemistry,
Institute of Chemical Technology (Autonomous),
Nathalal Paarikh Marg, Matunga (East),
Mumbai- 400 019, State of Maharastra,
India
27

Abstract
The invention concerns the field of surface active agent, in particular a novel surface active agent in the class of sugar fatty acid esters in solid, semisolid or liquid form, suitable to use in edible, pharmaceutical, agrochemical products. The invention also concerns a method for preparing said inventive novel surface active agent in the class of sugar fatty acid esters, produced in a single step process, comprising the step of reacting sugar, fatty acids and bifunctional acidic epoxide in the presence of a solvent, a catalyst (without using water, esters of fatty acids and fatty acyl chlorides).
To,
The Controller of Patents,
The Patent Office,
At Mumbai.
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Documents:

1177-MUM-2006-ABSTRACT(25-7-2006).pdf

1177-MUM-2006-ABSTRACT(5-6-2009).pdf

1177-MUM-2006-ABSTRACT(GRANTED)-(22-1-2011).pdf

1177-mum-2006-abstract.doc

1177-mum-2006-abstract.pdf

1177-MUM-2006-AMENDED CLAIMS OF SPECIFICATION(3-11-2009).tif

1177-MUM-2006-CANCELLED PAGES(3-11-2009).pdf

1177-MUM-2006-CLAIMS(25-7-2006).pdf

1177-MUM-2006-CLAIMS(3-11-2009).pdf

1177-MUM-2006-CLAIMS(5-6-2009).pdf

1177-MUM-2006-CLAIMS(AMENDED)-(3-11-2009).pdf

1177-MUM-2006-CLAIMS(GRANTED)-(22-1-2011).pdf

1177-mum-2006-claims.doc

1177-mum-2006-claims.pdf

1177-mum-2006-correspondence received.pdf

1177-MUM-2006-CORRESPONDENCE(25-7-2006).pdf

1177-MUM-2006-CORRESPONDENCE(3-11-2009).pdf

1177-MUM-2006-CORRESPONDENCE(5-6-2009).pdf

1177-MUM-2006-CORRESPONDENCE(IPO)-(24-1-2011).pdf

1177-mum-2006-description (complete).pdf

1177-MUM-2006-DESCRIPTION(COMPLETE)-(25-7-2006).pdf

1177-MUM-2006-DESCRIPTION(COMPLETE)-(5-6-2009).pdf

1177-MUM-2006-DESCRIPTION(GRANTED)-(22-1-2011).pdf

1177-MUM-2006-FORM 1(25-7-2006).pdf

1177-MUM-2006-FORM 1(5-6-2009).pdf

1177-MUM-2006-FORM 18(25-7-2006).pdf

1177-mum-2006-form 2(5-6-2009).pdf

1177-MUM-2006-FORM 2(COMPLETE)-(25-7-2006).pdf

1177-MUM-2006-FORM 2(GRANTED)-(22-1-2011).pdf

1177-MUM-2006-FORM 2(TITLE PAGE)-(5-6-2009).pdf

1177-MUM-2006-FORM 2(TITLE PAGE)-(COMPLETE)-25-7-2006).pdf

1177-MUM-2006-FORM 2(TITLE PAGE)-(GRANTED)-(22-1-2011).pdf

1177-mum-2006-form-1.pdf

1177-mum-2006-form-2.doc

1177-mum-2006-form-2.pdf

1177-mum-2006-form-3.pdf

1177-mum-2006-form-5.pdf


Patent Number 245507
Indian Patent Application Number 1177/MUM/2006
PG Journal Number 04/2011
Publication Date 28-Jan-2011
Grant Date 22-Jan-2011
Date of Filing 25-Jul-2006
Name of Patentee MANOHAR R. SAWANT
Applicant Address DEPARTMENT OF CHEMISTRY, INSTITUTE OF CHEMICAL TECHNOLOGY (AUTONOMOUS), NATHALAL PARIKH MARG, MATUNGA (EAST), MUMBAI 400 019,
Inventors:
# Inventor's Name Inventor's Address
1 MANOHAR R. SAWANT DEPARTMENT OF CHEMISTRY, INSTITUTE OF CHEMICAL TECHNOLOGY (AUTONOMOUS), NATHALAL PAARIKH MARG, MATUNGA (EAST), MUMBAI 400 019,
2 VISHAL. Y. JOSHI DEPARTMENT OF CHEMISTRY, INSTITUTE OF CHEMICAL TECHNOLOGY (AUTONOMOUS), NATHALAL PAARIKH MARG, MATUNGA (EAST), MUMBAI 400 019,
PCT International Classification Number C07H13/06, C11C3/04, C11D3/06
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA