BE544234A - - Google Patents

Description

       

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   The present invention relates to new esters of carboxylic acids of sucrose or raffinose and to processes for manufacturing these esters. More particularly, it relates to a new process for manufacturing esters of sucrose or raffinose and of fatty acids. about 6 to 30 carbon atoms, and it is also aimed at esters obtained by this process.



  'Bile also relates to new detergent compositions containing these esters and to new methods of washing, reducing the surface tension of surfaces and preparing emulsions, etc., using the esters targeted by the invention. invention.



  It relates particularly to mono- and di-sters of sucrose or raffinose-

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 The invention thus aims to achieve:
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 - new esters and preferably mono- and di-C'stet "'3 of sucrose or raffinose and di-fatty acids, ui constitute nonionic solid suchio-2ctifs agents CO"' ille detersives, wetting agents, emulsifiers or dispersants; these agents being moreover, in accordance with the invention, produced
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 inexpensive from raw materials or available in abundance and at low cost.



   - detergent compositions containing these agents; - new esters of this type exhibiting toxicity
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 extremely weak and not irritating the head, the eye and the mucous membranes of man, and which are edible because of the .syst5, * not digestive of the no '' '1' '': e hydrolyses them into food substances consisting of sugar and fatty acids; - a new efficient process for economically burning fatty acid esters of sucrose or raffinose, especially mono- and di-esters, with excellent yields and in a relatively pure form substantially free from impurities consisting of other esters.



   In recent years active research has been
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 company in the field of synthetic surfactants pn particular in the field of -synthetic detergents. Despite the great extent of research, few nonionic surfactants are found commercially which are solid. Those which are found feel comparatively expensive and possess * limited detersive properties.



   Nonionic surfactants have certain
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 ! 1r0) T'iltr c1sir ::: - l'les sp use in the c (3 o! -. I rinse detergents For example they are compatible 3. at the same time with frents 't'f: 5' ? Sti- crtion.i "" l1 <: S -t rZnri.C'135.

   They :: '.'- Y! 1.'t tolerate 1 "-; -, r'C: 0'Y! R> cfloi-Uî and magnesium ions which are found in rinsed waters f: c-.Y1S a r2.1J f ± Tré nde nesure, ": '. 10 ne le p0Tlv' - 'nt l, s r.fpntp t0r.i.C'-

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 active anionioues. they are less dependent on phosphate hydrides than anionic surfactants for their good detersive properties, and also they tend to be castor less strongly absorbed on the substrate than both anionic and cationic surfactants.



   It is desirable that the surfactants be solids rather than liquids, especially in the case of household detergents, since they can easily be mixed with the inorganic salts and putres ingredients used in the detergent compositions, for the cleaning. production of easily flowing powders and dry beads or grains by spraying. Surfactants possessing these properties allow the production of detergents at a lower cost per kilogram and also the final product can be packaged and delivered adequately.



   The fatty decide mono- or di-esters of sucrose or raffinose made in accordance with the process of the invention suitably combine all of the desirable properties listed in the discussion above and can be produced efficiently and inexpensively. following this new process'
In addition, the mono- and di-esters of fatty acids of sucrose are suitable for use in foods intended for human and animal consumption.

   This constitutes an important advantage of these esters since many of the previously known surfactants are subject to criticism of administration because of their dangers of toxicity or other side effects or irritant properties. The mono-esters of fatty acids of sucrose produced in accordance with the process according to the invention are entirely non-toxic and -snt more water-soluble than the mono-esters of fatty acids of glycerol which have hitherto been the surface-active agents. of choice for products intended for human consumption. The

  sucrose esters once absorbed,

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 are hydrolyzed by their constituents, raw acid and sugar, in the digestive tract .. and are they well tolerated? vav the body h1L-'¯ -, ':. ¯n meaning negative side effects. The 8cccII ± .rose diesters of a crude acid are less soluble in water and are a zero-dose type which was not previously available.



  As a result of the advantageous properties of the di-fatty acid esters and di-esters of sucrose in accordance with the invention, they can have very wide applications in the dominance of surfactants. For example, because of their pleasant taste and their high taste and digestibility, and their high food value, these esters should be widely used.
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 in food products. They can be used for '
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 cream sauces tie spic'de and condiments and other products.
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 food, non-acidic * By using them it is possible to emulsify the chocolate without first eliminating its excellent
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 butter decaC110 ('' '' me 'it is this current nrtiue currently.



  When used in the diet of people who have a certain difficulty 1. digesting fats, especially to envy people or very young children, it appears to have had absorption fat in the digestive tract is found
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 facilitated.



  The mono-esters of fatty acids according to the invention can
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 be used cOPl-'e detergents for different purposes They do not irritate the sensil'l '-! -., and the Te = u nor the nucous and this. made are well tcll r¯rFS for the body de l'l "" # -: - e or; le 1 ¯n¯i'¯.1 We can l ") 'f ..; r"} enter' rts r'1 {tersive for the toilet or''cour la 1>, siTr T P'ff>!>! i "n. '' '. fy, 'mt'J'!, l - 7nt ':! ". ê gelt'! e:?: '' t10r: 0'1 1'1: ct.r: rio; ::; t: - ti "ue.



  We prauto incorporate them in SC: 1F1r-oJin,! S yes do not produce <: l.1C'l11. '"1.'¯'" '1.t-' t? ^ n of the eyes of conS0 '1 ".: - tt" 1 ..:' r. The e: Y ': "8S il rasir, Fcvons ç iq,.;'. T-ßtiES =; t! TF-rSf'S utiTirrrit nng es + ors do not produce s:, S; 'il, t¯nt F'2C ¯I11 'skin irritation and' "! Ras rt) t7zzr? YSS. l.Jr: s fruits 0 the smokes can be whole1 ", nt 0e:> ttl) yi svcc cn?

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 esters without altering their taste, and the residues left are without adverse effect.

   When these edible and palatable laundry detergents are used they are not really affected by the hardness of the water * When used to lift dishes, it is not necessary to wipe them completely since if there happens to be a small amount of detergent left on the dishes when they are dry, there is no unpleasant reaction from the person using it.



   The mono- and di-esters according to the invention can also be used in the preparation of pharmaceutical products such as emulsions, toothpastes. When used in toothpastes they do not impart any bad taste or odor to the product as is the case with soaps manufactured today and certain synthetic detergents. Consequently, toothpastes containing these monoesters are not only perfectly suited to their use but are intended in particular to please the consumer because they have no unpleasant odor or FOOT.



   The mono- and di-esters according to the invention can be used to prepare feed rations for poultry, large cattle, and pigs in order to improve the digestibility of these rations.
Sucrose diesters are useful as demulsifiers, emulsifying agents. agents to avoid projections dan oils and fats for frying, to prevent hardening of the bread, and as lubricant.



   Ester them? according to the invention can be employed for the dry recovery of oil or petroleum, using aqueous solutions of these esters to displace the oil remaining in the subterranean rock, thereby allowing more efficient recovery of the petroleum in ground.



   The invention relates to esters of fatty acids, and in particular mono- and ni-esters, of sucrose or of raffin.

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 manufactured in accordance with the new process according to the invention and
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 wherein the fatty acid moiety of the esters contains approximately 8 to 30 carbon atoms, inclusive, and preferably about 12 to 22 carbon atoms inclusive. A particular subclass for use as wetting agents is suitably formed by the diesters having 6 to 12 carbon atoms in the fatty acid moiety.

   Among the fatty acids capable of constituting the acid-gres fraction of the mono-esters of sucrose or raffinose, are the saturated fatty acids
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 among which are the acids theiricue, rristiuue, palmitiaue, stearic, etc ... and the unsaturated fatty acids and preferably the unsaturated mono-fatty acids among which the acids # 9, 10
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 dodecliniaue, palmitoléiaue, oleiou, ricinoleit, etc., or mixtures of these acids.



   For the purpose of the invention, it should be noted that among the acids which can form the acid fraction
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 fatty, higher molecular weight carboyl balances deriving from natural products, such as products called acids
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 softwood obtained from rosin. to tall oil.



  The main constituent of coloph.ne'.as: lucid abiotic and sor anhydride yes make about 80% - 90 of ic co7.or¯rnn, and not 50 of t? Ll oil consist of acids of structure 2n. However, preferably, the products targeted by the invention are fatty acids and di-esters, often nélanges of fatty acids. fr.bricués c :::: ': 1.form 4. process according to the invention and mixed fatty acids obtained from (Ph "! 1i.los and fats F; IGI''l ^ tlpS yes meet r 'lflns nature. t1 ": among these glyceridic oils and fats we can cite: tallow, coconut oil, spermaceti oil, lard, lard oil, cocoa butter, palm oil, castor oil,

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 corn oil, olive oil, soybean oil, herring oil, menhaden oil etc ...

   The resulting mixed mono-and di-esters, containing the fatty acids initially present in the? oils and fats in the proportions relatively identical to those in which they are found in the starting oils and fats, and the final product appears to have properties superior to those of esters containing only one fatty acid-
The invention also relates to a new process for manufacturing the fatty acid esters of sucrose or raffinose.



  It consists in reacting with sucrose or raffinose a fatty acid ester of a product other than sucrose or raffinose. It is desirable to carry out the reaction in an aromatic, aliphatic, alicyclic or heterocyclic solvent having a group or an amide component or in a solvent formed by a heterocyclic or aliphatic tertiary amine, or a dialkyl sulfoxide, although in many cases a solvent can be dispensed with. The reaction mixture should contain an alkaline catalyst. Preferably, one operates under substantially anhydrous conditions since even a small presence of moisture can retard the rate of reaction.

   The reaction takes place by heating the mixture to a temperature ranging from about 20 C to about 180 C. The optimum temperature range is between 60 and 120. At lower temperatures the reaction products are less colored. The reaction time required is usually between 30 minutes and 24 hours, and depends to some extent on the temperature of the reaction mixture and the alkalinity of the catalyst, although a reaction time of. 2 to 5 hours.



   The fatty acid esters of? products other than bag @ harose and raffinoce used horn starting materials and

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 retort source of fatty acids may be simple esters of a monoalcohol, such as methyl palmitate, methyl stearate.
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 ethyl, ethyl ipurate, methyl 1-'F-biÉzt - ,, te, spread abietate etc .. or esters of - 'in:

  ., Qlirl (eo01 or polyol, in which the hydroxyl groups of alcohol are found on carbon atoms
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 adjacent, race the di- and tri-esters of glycerol *
It is preferable to use as the starting ester, an ester of a fatty acid and an easily volatile alcohol such as
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 mono-lower alcohols, methanol or ethanoli The volatile alcohol is preferably separated from the reaction mixture by distillation, if necessary under reduced pressure, as it is released during the formation of the sucrose ester or raffinose.

   This allows a faster reaction and gives higher yields of sucrose or raffinose esters, and achieves a separation of the volatile alcohol from the reaction solvent and the reaction products * When it is desired to use acids
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 mixed fat, retort 1 year old raw cs found in mixed glycerid esters found in nature, it is preferable
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 to first convert the plycéridin-s esters into mixed esters of a volatile alcohol, by regulating the glyceridin esters with the alcohol to carry out a transesterification 'instead of distilling under vacuum,

   the volatile alcohol can be removed from the reaction mixture by heating the mixture substantially with passion
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 atmospheres a temperature close to the boiling point of alcohol, and by making circulate in the system an i-inert gas ',, Co': 1 "r? -. ^ the Iron or nitrogen, not aroused. ble to react appreciably with the products in reaction or the products obtained.



   Among the suitable solvents which may be employed
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 for the reaction, there are ':.? 1 8' er'i: ¯ī ^ .1 "ES such rue: triR" th "'lFr''ine tri j-mç-ïlr'¯O?' T1 [11n¯ ', pyridine, - # "uinolélir.e, T> yrrci9,' éthylpyra '" ine I-drathylpiDrine, etc.



  C3, E! r3nfi such formami-, Ie; t¯! 'î¯.ftLrrl ClrP? i'1 such aids' - "e: foria.Tlide, f 2-pyrroli'-' ?.

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    N-methyl-2-pyrrolidone, etc ... Dinethylsulfoxide is an excellent
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 solvent. Other methods can advantageously be used. The solvent employed may contain other additional polar groups in the molecule, although groups such as mercapto, hydroxyl, primary and secondary amine ester groups should preferably be discarded. It is desirable that the amine or amide have no more than 6 carbon atoms per nitrogen atom present in the molecule, and the total number of carbon atoms should not exceed 12. Preferred solvents currently employed are 1
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 N, N-dimcthylformamide and dimethylsulfoxide- It is preferable to use a solvent less volatile than the alcohol of the starting ester.



   Among the alkaline catalysts likely to be
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 used are various types of metals, hydroxides, mineral salts and compounds. organic, among which there may be mentioned alkali metal hydroxides known hydroxides' of potassium, sodium and lithium, salts of an alkali metal and of a weak acid, such as
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 sodium carbonate, potassium carbonate, etc ... or alkalis such as trisodium phosphate;

     or alcoholates
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 alkalis, such as sodium methoxide, potassium ethylate, sodium ethvlate, or organic bases, such as bases
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 tarnished ammonium among which the mixed hydroxides c3rl-r? -7inÉ thvl-benzrl ammonium, the hydroxides of alkyl-trimethyl n'11J'oniut1 and the hydroxides of arioniun. cuatrnaire, tetra-alkylated, such as 'hydroxide of tetra-m (t! J ammonium, hydroxide of cetyl-di ", fthyl-'hpn7; Tl é11: Jr':. oniu: r, etc ... or alkaline sugars or raffinates, cojimes the sodium sucrate, sodium raffinate, etc.



  In addition, Y: 1ttüw :, such as etnin and 7inc are used. Alkali salts and crystals, and in particular potassium carbonate are the preferred catalysts.



  In a way!?, N8rflc, the alkaline catalysts''nui are satisfactory are those yes are soluble in solvents

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 used and which give jhnolphthalein the characteristic magenta alkaline coloration, when added at a concentration of 1% (by weight per unit volume) in the solution of phenol-
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 phteleine at 0.5% (by weight volume) in one. solvent T'snfer. 1 It is equal parts by volume of, N-dimeth. = lforarnide boiled and water free of carbon dioxide.

   The solution of; h2nùl:. 'Ltel'¯n' is prepared by boiling the N, N-di; -: 1: 't: -. Y.:-lfoJ'mii1ide beforehand for 15 minutes to remove the amines volatile & We dissolve
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 a gra:! Ü11é of phenolphteleine in 100 cc of N, N-di.u; ' th {lformOllide boiled and 100 cc of carbon dioxide-free water are added. When 0.1 gram of the alkaline catalyst is added to 10 cc of the phenol indicator solution; hts¯ein thus obtained, it should give the color purple or magenta well known from alkaline solutions of phenolphthalein.



   When a reaction solvent is used which tends to evaporate at reaction temperature, or when the volatile alcohol is separated as it is formed, it is good to carry out the reaction in a closed pressure vessel.
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 One of the important c; rr.ctéristiaues of the process according to the invention consists of the yields. raised in sonodi- or poly-esters of sucrose or raffinose which can be obtained
The process makes it possible to arrive at the non-di- or
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 pol: / "- substitutes for sucrose or raffinose, depending on the mol ire ratio of sucrose or rc, finose for the ester of depprt -present ..



  This is true if the reaction mixture contains a ratio of three :: 1018% of sucrose, or devEnte, for a drop of unsecured ester, and if the alcohol is separated from the acid. mixture by cJ.isti11ztioD: 'with Twr (> measurement of its formation, the product obtained is appreciably one!: C'! 1f) -ster. If one uses a "" goose of scchn-rose for two .¯ol3s of an acid ester with a volatile alcohol, the final product is pre-prepared with a sucrose di-ester.

   The greater the proportion nol..re this the starting ester p. r report "1 sccbro nf} (tU 'ff - :, n0 <: 1" S'c:; <:> ct "ve'r: mt, 111: 1 <:: 4" L ve <- se1 "- "the":; rgT 'is, trusted, ¯

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 cation of sucrose or raffinose. By using sufficiently large proportions of the starting ester, it is possible to arrive at esters of sucrose in which several hydroxyls are esterified. It is also possible to first prepare a sucrose polyester and then react it with an excess of sucrose equivalent to a ratio of three to one, in one of the solvents mentioned above and in the presence of one. alkaline catalysts indicated above, so as to substantially force the pure mono-ester.

   For practical reasons, it is preferable to employ a ratio of starting ester to sucrose of.



   1: 2 to 1:
From the data currently available, it appears that the reaction mechanism to which the process according to the invention makes use is based on the initial conversion of sucrose or raffinose into sucrate or raffinate anions, respectively. This conversion can take place in the reaction mixture under the effect of the alkaline catalyst. It appears that the alkaline catalyst combines one of the hydrogen ions of the hydroxyls of sucrose or raffinose with an alkali anion to form the sucrate or raffinate anions respectively. The sucrate or raffinate anion then appears to react with the fatty acid ester to form the fatty acid mono-esters of sucrose or raffinose according to the invention and an alkoxyl anion.

   The alkoxyl anion then takes a hydrogen cation giving rise to another sucrate or raffinate anion which continues the chain of the reaction. Part of the supplied picrate or raffinate anions is depleted during the operation. Confirmation of the mechanism suggested herein is found in the fact that alkaline sugars are satisfactory catalysts for the process.



     In this description, the terms sucrate and raffinate denote the anions formed by replacing one of the hydrogen ions of one of the hydroxyl groups of saceharose or raffinose respectively.

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  Of course, the invention cannot be limited by any theory or explanation one could give of it, it appears that the present. process allows the selective esterification of the p; rouj "'r, hydroxyls in the sucrose molecule Structural analysis of the sucrose monoesters produced in the following process
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 the invention indicates the z esterification. predominantly on the hydroxyl rump po and! ur the; carbon number 6 of the glucose part of the clecule (l- saren, .re.

   When a king-zester is produced conforming :: êm. = ¯i to iz2verft¯¯: n, one of the ester groups is placed predominantly at (the hydroxyln the carbon atom nuuero 6 of the glucose moiety and lY4.!. T "is sensitive, formed predominantly at the d-1-llirdroxyl level attached to carbon atom number 6 of the fructose moiety of sucrose.



   The invention also includes several efficient methods of recovering and purifying the sucrose esters obtained by the procedure * In some cases, when making a
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 mono-ester of sacchr nse, it suffices to distill the solvent to separate it from the melBnF 'r6;:. ctional, and obtain a dry residue containing, by weight, substantially equal proportions of the mono-ester and of the sucrose not entered into the reaction. We hardly find anything else
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 ,.: 1. y the product if this 't' .ost a low percentage of alkaline catalyst, of the order of laà. 2% in weight.



   This product is suitable for many applications - including uses as detergents, meaning other purification. In some cases, it is desirable to recover the sucrose for recycling in the process. This can be achieved by dissolving the dry residue remaining after distillation in three or four times its weight of water and then adding about 5% sodium chloride calculated on the amount of water. We can heat the mixture
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 around 80-900C and keep it at that temperature until. That the sucrose mono-ester binds Gl; p # e in a separate layer. The nc, nr-e layer is separated;

  r sucrose gru1f '> 1't. "(and che. r." t.t <3 layer usually contains about 50 to 60i of soli-

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 of which about 80 to 85% are soluble in alcohol. @e remainder is formed of sucrose and sodium chloride. The aqueous layer yes then contains most of the non-reacted saceharose can be evaporated and the sucrose and sodium chloride can be recycled. in the process *
Sucrose and sodium chloride can be completely removed efficiently by distributing the solids. obtained after distillation of the solvent, between a 5% sodium chloride solution and n-butanol.

   The butanol layer is separated and the butnol is distilled off, the resulting product contains about 90% sucrose monoester * The remainder is soap and sucrose polyesters. It can be recrystallized from 'acetone this product at 90% purity to obtain the pure sucrose monoester
When making a sucrose di-ester, the residue remaining after simple distillation of the reaction solvent contains more than 90% pure sucrose di-ester. In general, there is no need for further purification for most commercial applications.



   Another process for the purification of the sucrose monoesters obtained in the reaction described above in the case where an amide or a tertiary amine is used as solvent, is as follows. Although the details of the process vary depending on the specific nature of the solvent or reagents employed, it generally involves distilling off an appreciable amount of the solvent, such as 1/4 to 3/4 of the volume employed, and preferably half of the solvent. volume employed; the residue is then cooled, preferably around 20 to 30 ° C. II. As a result of this cooling, the decided fatty esters which have not entered into reaction and used as deporting esters are separated from the residue.

   This is particularly true of the fatty di- and tri-esters of glycerol and the fatty acid esters of monoalcohols, which have not reacted, which are not reacted.

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 be. The sucrose mono-esters formed, and part of the glycerol mono-esters which can form, as well as all the salts of free fatty acids, remain dissolved in the solvent. The degree of purification obtained is suitable for many commercial applications of sucrose monoesters.

   However, a still further degree of purification can be achieved by extracting the resulting solution with a solvent consisting of an aliphatic hydrocarbon, preferably a lower saturated alirhatic hydrocarbon such as hexane or pentane. This method of treatment makes it possible to extract from the solution the last traces of aon-saccharic esters which have not entered into reaction. The remaining solution is distilled again to a small volume and then diluted with several volumes of a polar solvent such as acetone or butanol, to precipitate the unconverted sucrose. The latter is filtered and a clear solution of the spccharose mono-ester is obtained.

   This solution is evaporated by distillation and the residue obtained constitutes a commercially pure sucrose mono-ester. The best results are obtained in this purification by using as reaction solvent formamide, -methyl-2-pyrrolidone or N, N-dimethyl-formamide, and in particular the latter solvent.



   In order to better understand the nature of the invention, some specific examples are given below,
Of course, they cannot limit the invention to the particular details mentioned and they are given only by way of illustration. In the examples which follow the term "conversion yields" denotes the ratio of sucrose converted to ester relative to the sucrose not recovered from the reectional mixture in a form suitable for recycling. The parts are expressed by weight.

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 aYr =:. =. rz 100 pramwos (0.293 moles) of sucrose are dissolved in 1..00 cc of, Il-di.vth, -. rl-fCrnl "eie en r.lf..18np '<;: lnt these products and heat 1, '; re ,, ent.

   To the resulting solution were added 173 grams (0.195 moles) of tristearin and 1.0 mg of sodium methoxide.



  The 7cf.l ['Yl is heated for 3 hours in a closed reciter, at about 115 -155 C. Then distilled off about 1a. half1 of the dimth.vlforna: nest of the functional mixture * One cools 1 residue 1. a 'temperature included rY'1!, T'oximf1tive'Tlent' ènt1. "'o 20 and 30 C nt on s, -, -r" ; .-, 'f - ,,' lfpr'nelt? lir7e l: t> istp; 'rinE (. non trIDsfn: r "' rI'e and cit¯rine resulting from the reaction el'cn them sÓpcr0 by filtration .

   The solution obtained is extracted with
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 several times its volume of normal hexene and evaporated by
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 distillation j11sau 'à. get a thick syrup. an addition of acetone to the solution of di'nr'thylformamide and this has the effect of precipitating the non-tronsfne sucrose street is recovered by filtration The content of sucrose mono stearate collected by éVé'POrf + 'ion of If ecetoninium solution (c1Uiv & ut at a yield of 20: &, 3 /; 'nu spcr'11.-rosc starting nn transformed * FXF. "PLF. II.



  Preparing a solution of (about 14.qiolvrnt, 100 rnm8S (0.293 mol) of sucrose in 440cc of ludithylforrnmice and there is r1 (1'mn'9 z PTPT1Fres (0.147 mol) of ci stétître, 0isson + 'A (Jans 300 cc of N, N-d3.s. ^. Rtr'l.forman! Ide. We place the? Nlwn; e r8sul tr: nt in a? 1 (pressurized Yrlne containing about 3 gr ['("ps of '1.' sodium hydroxide pt nn heats the rO "1be lndant c: TTir. On 15 hours at around 16C C. The solvent (: -lj. '", Ethyl-rn "' Qf1- nidp) by.-¯7 tlr, n or vir'te. un cools the remaining solution rr "...- j'l" 3.sT ^; ', nr f la' tC ': JE'¯ "é' t ".].? 'n'Y> r1nr--!" "" "'" r., .. ",,,, (it: 10j 1'- r? i stF'r.rir, not transformed rrÉ 'ci'Ji tC'. We sr'r-rP le p-rfcJ "Ji t / rrtr

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 filtered. tion, and the filtrate was extracted three times with equal volumes of hexane.

   The residue in dimethylforma! Nide is then concentrated by vacuum distillation to a spicy syrup, which is precipitated with acetone. The acetonine solution is evaporated to give a. residue composed of 22 <ram: 'es (0.036 mol) of relatively pure sucrose momstearate exhibited a melting point of about 520-53 ° C a (2 - - + 33.2; absolute yield of 2.4.6 The untransformed sucrose obtained previously is filtered and dried for use in subsequent operations. It has been found that the nonostea-r, -.
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 Pure sucrose has the following constants: melting point
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 52-53 C and [* 31 # + "39.35. EXAMPLE III.



  We prepare a suspension solution for about 100 grains
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 (0.293 mole) of sucrose in. 600 cc of pyridine * Mix
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 to this suspension about 173 seeds (Of195 mole) of dissolved tristrrine with 3 fl0c of pyridine * To the mixture are added about 5 prrrvnes of sodium, after which the mixture is ebe-uffed in a closed pressure bomb for 15 hours at a
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 temperature of about 150 ° C. Most of the reaction mixture is evaporated off per + ie. pyridine by vacuum distillation and
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 dissolves! "when the residue drns a minimum of rll: .- Iétb7'lfnr-i, -. micle.

   The pn1liticn resultpntp a "once cooled below the terip''rrture where ^ c? Īni rP, it is free, t the filtrate is extracted twice with TO'¯t ':" S cf vx of h en, and 1- solution remaining pros extraction is diluted with five times S ^ .n v01'U! a 2Cé t0''le Sucrose not entered into reaction '^ ¯r? CTï'i' 1aA dors du filtrate and n 1 collects '"' -r fil i, -. i0: 'l .. The titrate in tonic is then sv norr Piccité and' 'ine 35 r? -'" es (0;, 05 no'La) d @ r! 'nr; st' '' '^ r' ç'¯'r'C-'f'v'r7ßE '=' 't8.1 "5i- to a rrn'" 'f : "'. on" 1 "of .29.5 *

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 calculated with respect to the quantity of tristearin involved.



  EXAMPLE IV.



   A solution is prepared by dissolving about 100 grams (0.293 mol) of sucrose in 500 cc of N, N-dimethylformamide. To the resulting solution, about 170 grams (0.195 moles) of edible tallow, a commercial fat usually obtained from beef tallow, is added. (Tallow contains fatty acids distributed approximately in 25% palmitic, 24% stearic, 42% oleic, 2% myristic, 2% palmitoleit without taking into account the rest of the fatty acids entering into the composition of this tallow).

   About 3 grams of sodium methoxide is added to the resulting mixture, and the mixture is then placed in a pressure canister, and heated in this canister for 15 hours at about 140-150 C. Evaporate about half of the mixture. dimethylformamide by vacuum distillation and the non-reactive fat is allowed to separate which is then removed. The remaining solution in dimethylformamide is purified according to the method described in Example II. The amount of the saccharic mono- derivative of the tallow collected corresponds to a conversion yield of about 25%. 'EXAMPLE V.



   The operations of Example IV 'are repeated with the difference that the tallow dissolved in dimethylformamide is replaced by a solution of approximately 116 grams (0.175 mol)' of coconut oil dissolved in 400 cc of N, N-dimethylformamide. (The coconut oil in question contains a fatty acid content of approximately 45% lauric acid, 18% myristic acid, 10% palmitic acid and 8% oleic acid.

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  The rest of the fatty acid c-composition is made up of small percentages of other saturated and unsaturated acids).



  Approximately 35 grams (0.066 mol) of monosaccharic fatty acid derivative of coconut oil are obtained, with a yield of approximately 37.5% calculated relative to the quantity of oil used. C EXAMPLE VI. -
70 grams (0.208 mol) of sucrose are dissolved in 400 cc of N, N-dimethylformamide. 92 grams (0.14 mol) of tristearin dissolved in 400 cc of dimethylformamide are mixed with the resulting solution. The mixture is placed in a pressure bomb with 3 grams of trisodium phosphate. The bomb is heated for 8 hours at a temperature of 1SO C.



  Half of the dimethylformamide is removed by distillation and the sucrose monostearate is collected as in Example II. The amount of substantially pure sucrose monostearate collected corresponds to a conversion yield of the order of 29%.



  EXAMPLE VII.-
About 100 grams (0.293 moles) of saccharose is dissolved in 500 cc of N, N-dimethylformamide. About 62 grams (0.20 mol) of methyl laurate dissolved in 400 cc of dimethylformamide are mixed with this solution. About 2 grams of sodium methylate are added to the resulting mixture and the mixture is placed in a pressure canister in which it is heated for 8 hours at a temperature of about 130 ° C. in the closed canister. The reaction mixture is distilled to halve its volume and the residue cooled. On cooling, the unreacted methyl laurate separates and is recovered.

   The remaining solution in dimethylformamide is extracted twice with equal volumes.

 <Desc / Clms Page number 19>

 of hexane, after which an amount of acetone equal to five times the volume of this solution is added to the solution in dimethylformamide. The product which then precipitates from the resulting solution in the acetone-dimethylformamide mixture is separated by filtration, and the filtrate evaporated by distillation to finally give a residue which, when recrystallized from acetone, gives
30 grams of sucrose monolaurate (melting point: 72 -80 C; 22 [Ó] D = + 52.0) giving a conversion yield of about 50%.

   Pure sucrose monaurate was found to exhibit the following constants: melting point = 90-91 C and [Ó] 20 = + 42.5.



  EXAMPLE VIII. -
The operations described in Example VII are repeated, replacing the methyl laurate with approximately 87 grams (0.294 mol) of methyl oleate. Sucrose monooleate is obtained by this process in an amount corresponding to a yield of 17%.



    EXAMPLE IX. -
200 grams (0.397 mole) of pre-dried raffinose are dissolved in 800 cc of dry N, N-dimethylformamide.



  190 grams (0.263 mol) of coconut oil are added to this solution. The resulting solution is heated to 90 ° C. and maintained at this temperature for 12 hours with constant stirring. During this time sodium methoxide was added as a catalyst in four 1 gram portions. At the end of the reaction, the solution is extracted four times with equal volumes of hexane. The dimethylformamide solution was concentrated by distillation under a vacuum of 1.0 mm of mercury until a thick syrup was obtained. This syrup is diluted with seven volumes of acetone and the resulting suspension is thoroughly mixed.



  The unprocessed raffinose which precipitates is leached with the acetone solution for four hours. The suspension is filtered and the insoluble residue is extracted with n-butanol.



  The butanolic extract is added to the extract

 <Desc / Clms Page number 20>

 acetone and the combined extracts are distilled until solidified. The raffinose and fatty acid derivative of coconut oil thus obtained is dried completely and gives 85 grams of product.



  EXAMPLE X.



   About 100 grams (0.293 mol) of sucrose are dissolved in 400 cc of N, N-dimethylformamide. To this solution are added 62.5 grams (0.293 mol) of methyl laurate and 2 grams of solid potassium hydroxide. The resulting mixture is heated to 90 -100 ° C in a beaker with a lid for 12 hours.



  After cooling, the solution in dimethylformamide is extracted five times with equal volumes of hexane. The solution in dimethylformamide is then distilled to half its volume and precipitated with 5 volumes of acetones. The sucrose which then precipitates is extracted with n-butanol. The butanol extract is added to the solution in the acetone-dimethylformamide mixture and the mixture of solvents is distilled to a thick syrupy consistency. At this stage, a new portion of sucrose is separated, and the filtrate is dried which gives 25.9 grams (yield 16.9%) of sucrose monolaurate; [Ó] 2D = + 47.6.



  EXAMPLE XI.



   About 100 grams (0.293 mole) of sucrose and 62.5 grams (0.293 mole) of methyl laurate are dissolved in 400 cc of N, N-dimethylformamide. 10 grams of cocoyltrimethyl ammonium sucrate is added as a catalyst, prepared by adding 4.4 grams of cocoyl trimethyl ammonium hydroxide to 5.7 grams of sucrose in 20 cc of dimethylformamide and evaporating all the solvents by distillation. to arrive at a dry product. The resulting solution is heated at 90 ° -100 ° C. for 12 hours in an open beaker in the open air.

   After

 <Desc / Clms Page number 21>

 After cooling, the solution in dimethylformamide is extracted five times with equal volumes of hexane. The formalin solution is then distilled to 1/3 of its volume and precipitated with 5 volumes of acetone. The sucrose which precipitates is filtered off and the solution is distilled in an acetone-dimethylformamide mixture to dryness and 40 grams of sucrose monaurate are obtained.



   In each of the preceding examples, the starting unreacted non-saccharic fatty acid esters are almost completely recoverable in a form suitable for recycling to the process or for other commercial uses.



   EXAMPLE XII.



   Working with completely dry products, a solution of approximately 387 grams of sucrose in 1275 cc of dimethylformamide is made with heating and vigorous stirring.



  112.5 grams of methyl stearate and 7.5 grams of potassium carbonate are added to the solution. The resulting reaction mixture is maintained at 90 -95 C under a pressure of 80 to 100 mm of mercury. Methanol produced during the reaction is removed from the system as it is formed by means of a 6-plate fractionation column. After 9 to 12 hours, part of the dimethylformamide is distilled off and the residue is dried in vacuo. The dry residue was found to contain 53.9%. Sucrose, 37.9% sucrose monostearate, 1.6% sucrose distearate, 0.0% methyl stearate, 2.9% potassium stearate, and 1.3% potassium carbonate.



  EXAMPLE XIII.



   Sucrose monostearate is prepared using high concentrations of reagents in dimethyl sulfoxide.



  The reaction mixture consists of 150 grams of st @ arate

 <Desc / Clms Page number 22>

 of methyl, 516 grams of sucrose, 350 cc of dimethyl sulfoxide and 15 grams of potassium carbonate. After 7.5 hours at 90 ° C, 100 mm Hg pressure, and sweeping the system with dry air free of carbon dioxide, the methyl stearate is converted entirely to substantially equal part in the weight of monostearate. and sucrose distearate.



  EXAMPLE XIV.



   In this example is described the preparation of sucrose monostearate at a temperature of 120 C. The reaction mixture is formed of 387 grams of sucrose, 112.5 grams of methyl stearate, 1275 cc of dimethylfornamide and 7.5 grams. potassium carbonate. The reaction is carried out at 120 ° C., under a pressure of 190 ° to 195 mm Hg, and a stream of dry air free of carbon dioxide is bubbled through the reaction mixture. After one hour, 75 percent of the methyl stearate and 75 percent of the theoretical amount of sucrose to form the mono-ester were found to have reacted.

   After two hours 80 percent of methyl stearate and 78 percent of theoretical sugar has reacted to form sucrose-mono-stearate EXAMPLE XV
In this example, the preparation of the sucrose monoester of tallow fatty acids is described. The reaction mixture is formed from approximately 112.5 grams of methylated derivative of tallow fatty acids, 387 grams of sucrose, 1275 cc of dimethylformamide, and 7.5 grams of potassium carbonate. The reaction mixture is sensiblerent anhydrous.

   The methyl derivative of tallow fatty acids is obtained by subjecting the tallow used in Example IV, above, to transesterification using methyl alcohol according to conventional methods, with subsequent elimination of the formed glycerol. After heating the mixture for

 <Desc / Clms Page number 23>

 
12 hours, at 90 -95 C, under a pressure of 100 mm of mercury, without flushing the system with air, the distribution of tallow derivatives is as follows: 5.3% of methyl derivative of tallow not entered into reaction, 2.4% as soap, 66.4% as sucrose monoester and 25.9% sucrose diester.



   At the end of the reaction, the solution is distilled to remove about 90 percent of the diriethylforriamide. 500 cc of n-butanol and 500 cc of water are then added to the resulting paste.



   The mixture is heated with stirring until the solids have dissolved in the two liquid phases. The two layers are separated while still hot and the butanol layer is washed once with a further 500 cc of cold water. By analysis of the combined aqueous layers, it was found that 96.5 percent of the saccharic esters were collected in the butanol layer.



  EXAMPLE XVI.



   Sucrose distearate is prepared by heating a solution consisting of 150 grams of methyl stearate, 82 grams of sucrose, 15 grams of potassium carbonate, and one liter of dimethylformamide. The operation is carried out at 90 ° C., under a pressure of 100 mm of mercury, and by bubbling in the solution a stream of dry air free of carbon dioxide. After 12 hours, 97 percent methyl stearate has reacted to give a product containing, alongside the catalyst, about 95 percent sucrose distearate with the remainder being monostearate and potassium stearate.



  EXAMPLE XVII.



   Coconut oil saccharic fatty acid diester ("sucrose dicocoate") is prepared using a molar ratio of the fatty acid methyl ester of coconut oil (methyl cocoate ") 2: 1 sucrose.



  The reaction reaction is formed from 230 grams of methyl cocoate, 172 grams of sucrose.

 <Desc / Clms Page number 24>

 
680 cc of dimethylformamide and 15 grams of potassium carbonate. Methyl cocoate results from the reaction of coconut oil, described in example v, above, with methanol in order to produce transesterification by conventional methods, the glycerol formed then being separate. The mixture is heated to 90 ° C. under a pressure of 100 mm of mercury and a stream of dry air free of carbon dioxide is bubbled through the solution.



   After 12 hours all of the methyl cocoate had reacted except 4.5 percent. Approximately 5 percent of the methyl cocoate is converted into soap. Thus approximately 1.8 moles of cocoate are esterified per mole of sucrose resulting in the production of the sucrose dicocoate.



   EXAMPLE XVIII One mole of sucrose is reacted with additional moles of methyl stearate. The reaction mixture is formed from 600 graduas of methyl stearate, 172 grams of sucrose 850 cc of dimethylformamide, and 5.0 grades of potassium carbonate. The reaction mixture is heated for 12 hours at 90-95 ° C and 100 mm Hg pressure, without air bubbling through the system.



  Analysis shows that 2.0 percent of the methyl stearate has been converted to soap and 14 percent of the methyl stearate is recovered unconverted.



  Thus 3.3 moles of methyl stearate per mole of saccharosis reacted to give a polysaccharose stearate.



  EXEMPLEXIX
A - Working with completely dry products, a solution of 129 grams of sucrose in 425 cc of diaethylformamide is prepared with heating and vigorous stirring. To this solution are added 37.5 grams of ethyl stearate and 2.5 grams. of potassium carbonate. The reaction mixture is maintained at 90-95 C under a pressure of 80 to 100 mm of mercury. We splash around

 <Desc / Clms Page number 25>

 in the solution a stream of dry air, free of carbon dioxide, at a rate of approximately 100 cc per minute. A six-tray fractionation column system is used to separate the methanol from the system. After 10 hours of reaction, the mixture is distilled to dryness.



  Analysis of the residue revealed 76 grams of sucrose monostearate and 86 grams of sucrose.



   B - 300 cc of a 10 percent aqueous sodium chloride solution and 300 cc of n-butanol are added to a 100 gram portion of the residue of A obtained above. The mixture is heated with stirring until complete dissolution of the solids. The two layers are separated and the butanol layer is washed with twice 150 cc of 10 percent aqueous sodium chloride solution. The butanol layer is evaporated to dryness by distillation, and a solid residue is obtained containing 93 percent of sucrose monostearate.



   : EXAMPLE XX
The process described in Example XIX is repeated. The dry residue (170 grams) is dissolved in 680 cc of water with heating. 68 grams of sodium chloride are then added. Leave to stand overnight and separate the
 EMI25.1
 pité formed by filtration and dried. The residue contains 67 percent sucrose monostearate. The rest is made up of salt and sucrose. '
Other glyceridic oils and greases and other mono-alcohol esters can be used to make sucrose esters according to the process of the invention.

   More specifically, instead of the tallow employed in Example IV above, equimolecular amounts of one or more of the following glyceridic oils or fats can be substituted: oil
 EMI25.2
 ne! 7oerri, ceti., lard, oil 'the sqindouy, eight.'] "'r" cJd,' j0, cocoa butter, o'lm oil

 <Desc / Clms Page number 26>

 castor oil, corn oil, declive oil, soybean oil,
 EMI26.1
 herring oil, menhaden oil etc ...

   The mixed acid esters v: r ::> 8 of sucrose or rvfainose which c
 EMI26.2
 results have an acid content r! '. s cuti has relatively the same proportions as those originally encountered in the initial oil *
 EMI26.3
 Very legli-ns catalysts were employed instead of those employed in the examples described below.
 EMI26.4
 In particular, one can satisfactorily use ni-th7, riet of potassium, 1-ethyl-ate of potassium has other alkaline alcoholates, as well as alkaline sugars such as potassium sucrate. , and the 77 [of alkalis such as sodium hydroxide and lithium hydroxide).



   Instead of solvents used in the examples above. other solvents can be used. For example, excellent results are obtained by using the
 EMI26.5
 N-Biethyl-2-pyrrolidone or 1? 2-meth.ylpyr? .Zine. Solvent cops are particularly stable in the presence of catalysts
 EMI26.6
 strongly basic. Other amines, such as trimethylamine, are satisfactory, although when the amine has a
 EMI26.7
 Due to a high boiling point, doses should be taken to avoid loss of these products when subjected to higher t <;; rr..u.'r - "'tures. The option must then be closed to prevent loss of solvent.



  Preferably, the solvent should be less volatile than the alcohol of the starting non-scrub ester.
 EMI26.8
 



  Although the s-cch, 7rose used in the -) can not be introduced in the form of the products! L:> ins urs available as 5 '-) 1.1 S -}):' '' L ' '¯; Í t oe sugar refineries etc., loss'? 1 I''S res "'lt * ts are' ?? l:,:, !! it:,!.; S:; V0C les f ',!, "19S fonts Z''nl ^' W4 rf, -t pure 'iu- s" 1h "r'.) Se had? 'We. found in 'r T3 ^' ba.s price.

 <Desc / Clms Page number 27>

 



   As it was said previously, the mono-- and di-esters; sucrose according to the invention have excellent detersive, emulsifying, wetting and dispersive properties and can be used for a large number of purposes. In comparison with the previously known nonionic detergents they have superior properties. The sucrose monoesters according to the invention have excellent properties as detergents for human hygiene or for laundry, dishwashing, etc ... and the application of these esters for cleaning purposes. cleaning constitutes one of the important objects of the invention.

   When they are used for laundry, etc., the monoesters can be used in the form of a detergent composition with fillers or adjuvants, that is to say in a mixture with detergent auxiliaries such as to have a synergistic action with the detergents. detersive properties of the sucrose or raffinose esters according to the invention. As examples of these synergistic auxiliaries, mention may be made of the phosphates dehydrated in their molecule, alkali metal phosphates, silicates, borates, carbonates, sulphates and alkali metal chlorides. Sodium-carboxymethyl-cellulose is also a favorable compound in such a detergent composition.

   Detergent compositions containing 10 to 40% by weight of a sucrose or raffinose mono-ester constitute an important subject of the invention:
As examples of detergent compositions for coarse work, containing sucrose monoesters in accordance with the invention, the following may be mentioned.

 <Desc / Clms Page number 28>

 
 EMI28.1
 
<tb>



  Parts <SEP> in <SEP> weight.
<tb>
<tb>



  <SEP> number of <SEP> example <SEP> 21 <SEP> 22 <SEP> 23 <SEP> 24 <SEP> 25 <SEP> 26 <SEP> 27 <SEP>. <SEP>
<tb>
<tb>



  Sucrose <SEP> monoesters <SEP>
<tb> derived <SEP> from <SEP> tallow <SEP> (example <SEP> IV) <SEP> 20.0 <SEP> - <SEP> 20.0 <SEP> - <SEP> 20.0 <SEP > 15.0 <SEP> 25.0
<tb>
<tb> Mono-cocoate <SEP> of <SEP> sucrose <SEP> (example <SEP> V) - <SEP> 20.0 <SEP> - <SEP> - <SEP> - <SEP> -
<tb>
<tb> Mono-oleate <SEP> of <SEP> sucrose <SEP> (example <SEP> VIII) - <SEP> - <SEP> 10.0 <SEP> 25.0 <SEP> -
<tb>
<tb> Tripolyphosphate <SEP> from
<tb> sodium <SEP> 40.0 <SEP> 40.0 <SEP> 45.0 <SEP> 38.0 <SEP> 38.0 <SEP> 40.0 <SEP> 50, (
<tb>
<tb> Pyrophosphate <SEP> Tetrasodium <SEP> 10.0- <SEP> - <SEP> 5.0 <SEP> - <SEP> 8.0 <SEP> -
<tb>
<tb> Sodium <SEP> silicate <SEP>
<tb> (Na20 <SEP>: Si02 <SEP> = <SEP> 1: 3.2) <SEP> 5.0 <SEP> - <SEP> 4.0 <SEP> 6.0- <SEP> 5 ,VS
<tb>
<tb> Sodium <SEP> silicate <SEP>
<tb> (Na2O <SEP>: Si02 <SEP> = <SEP> 1:

  2) <SEP> - <SEP> 6.0 <SEP> 4.0 <SEP> - <SEP> - <SEP> 5.0 <SEP> -
<tb>
<tb> Sucrose <SEP> 22.0 <SEP> 10.0 <SEP> - <SEP> 5.0 <SEP> 5.0 <SEP> 2.0 <SEP> -
<tb>
<tb> <SEP> sodium chloride <SEP> - <SEP> - <SEP> 10.0 <SEP> - <SEP> - <SEP> 10.0 <SEP> -
<tb>
<tb> Sodium <SEP> <SEP> <SEP> 20.0 <SEP> 8.0 <SEP> 18.0 <SEP> 26.5 <SEP> 6.0 <SEP> 15.0
<tb>
 
 EMI28.2
 Sodium-carboxymthyl
 EMI28.3
 
<tb> cellulose <SEP> 0.5 <SEP> 1.0 <SEP> 0.3 <SEP> 0.5 <SEP> 0.5 <SEP> 0.5 <SEP> 0.5
<tb>
<tb> Humidity <SEP> 2.5 <SEP> 3.0 <SEP> 2.7 <SEP> 4.5 <SEP> 4.0 <SEP> 3.5 <SEP> 4.5
<tb>
 
 EMI28.4
 Dodecylbenzenesulf'Qnafis
 EMI28.5
 
<tb> sodium <SEP> - <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 10.0-
<tb>
 
The compositions listed above may also contain any of the shine enhancing agents commonly used in detergent compositions.

   The above compositions can advantageously be used in aqueous solutions at a
 EMI28.6
 concentration from 01% to Oi5% *
The novel esters of sucrose or of raffinose and of fatty acids produced in accordance with the invention may be supplemented with germicidal or bacteriostatic agents, in particular when these esters are used for the preparation of detergent soaps for the toilet.

   Among the germicidal and bacteriostatic agents that may be used, mention may be made of
 EMI28.7
 hexachl.orophene and quaternary ammonium salts such as alkyldir.jethylbenzylammonium halides sold under the brands

 <Desc / Clms Page number 29>

 Chlorides of "Zephiran", "Roccal", "Triton K-60" and "Ammonyx", and comprising: cetyl-dimethylbenzyl ammonium chloride, and octylphenoxyethoxy-ethyl-dimethyl-benzylammonium chloride (Hyamine). Other quaternary ammonium salts such as cetyl trimethylammonium chloride etc ... can be used.

   When a quaternary ammonium base is employed as a catalyst for the preparation of the monoesters according to the invention, it can be recovered from the reaction product and converted into an active quaternary ammonium salt by addition of a dilute mineral acid.



   Of course, the invention is not limited to the embodiments described which have been cited only by way of example.


    

Claims (1)

ABSTRACT The main objects of the invention are: 1 - A process for making esters of carboxylic acids of a saccharide chosen from the group formed by sucrose and raffinose, said process being remarkable in particular by the following characteristics considered separately or in combinations. a) the sucrose or raffinose, or the sucrate or raffinate anions, are treated with a carboxylic acid ester of an alcohol not constituting a saccharide; b) the carboxylic acid is a fatty acid containing 6 to 30 carbon atoms; c) it is a saturated or unsaturated carboxylic acid; d) the sugar or raffina anions are treated with a glycerol ester; e) these anions are treated with an ester of a carboxylic acid and a volatile alcohol; f) in particular, with a view to obtaining an acid monoester <Desc / Clms Page number 30> fatty sucrose, sucrose is heated with an ester of a carboxylic acid of glycerol or of a volatile alcohol in the presence of an alkaline catalyst; g) said volatile alcohol is a monohydric alcohol; h) said glycerol ester is a glyceride mix of natural fatty acids; i) the alkaline catalyst used in the reaction EMI30.1 produces the characteristic magenta coloration of phenolphtha: i.ne. when added at a concentration of 1% (w / v) EMI30.2 in a 0.5 (w / v) solution of phenolph; ;. aleihe in a solvent containing in equal volumes boiled N, N-dimethylformamide and carbon dioxide-free water; j) the reaction is carried out in an organic solvent chosen from the class formed by aromatic, aliphatic, alicyclic and heterocyclic amides, tertiary amines and dialkyl tallow oxides; k) the organic solvent consists of N, N-dimethylformamide; 1) the reaction is carried out at a temperature between 20 and 180 C; 2) as new industrial products: compounds, remarkable in particular by the following characteristics considered separately or in combinations: a) they are dicarboxylic mono- or di-esters of a saccharide consisting of sucrose or raffinose; - b ) the carboxylic acid contains 6 to 30 carbon atoms; c) the carboxylic acid is a fatty acid or a mixture of fatty acids; d) mono-esters are in particular: sucrose lemonostearate; monoester of sucrose and fatty acids from tallow or coconut oil; sucrose lemonoleate: <Desc / Clms Page number 31> sucrose mono-abietate; lemonoester of raffinose and fatty acids from coconut oil; the monoester of sucrose and mixed fatty acids of lard oil; sucrose mono-lauate; e) the di-esters are in particular: sucrose di-stearate; sucrose di-ester and fatty acids from coconut oil or tallow. 3) A remarkable detersive composition in particular in that it contains as active agent from 10 to 40% by weight of one of the fatty acid esters described above, optionally with a detersive auxiliary chosen from among the following: phosphates dehydrated in the molecule, alkali phosphates, silicates, borates, carbonates, sulfates, alkali chlorides and sodium carboxymethylcellulose, the composition possibly further containing a germicidal agent. 4) Inapplication for cleaning the fatty acid esters of the aforementioned saccharides in the form of aqueous solutions or of the aforementioned detersive compositions.