USRE21322E - Method of producing the same - Google Patents

Description

Reissue Jan. 16,

PATENT OFFICE INTERFACE MODIFYING AGENTS AND METHOD OF PRODUCING THE' SAME Benjamin It. Harris, Chicago, 11]., assignor to The Emuls'ol Corporation, Chicago, 11]., a

poration of Illinois No Drawing. Original No. 2,023,388, dated-December 3, 1935, Serial No. 754,087, November 21, 1934. Application for reissue 1939, Serial No. 249,820

January 7,

Claims. (01. 260411) My invention relates to new and useful improvements in esters of polyglycerols and method of producing thesame. My present invention is a continuation in part of my prior application, Serial No. 697,533, filed November 10, 1933, which in turn is a continuation-in-part of my prior application Serial No. 407,797, filed November 16, 1929, now Patent No. 1,958,700.

The polyglycerol esters of my present invenl tion meet a demand or need for certain materials having in general oleaginous or fatty character and also certain characteristics not ordinarily associated with fats; These characteristics may, in general, be summed up by the term hydrophilic property. This hydrophilic property,

however, is merely a broad generalization, as in different cases the characteristic is identified with the particular object or function desired in a particular art or industry. The polyglycerol go esters of my invention, quite apart from any consideration of their structure, possess certain characteristics and properties as emulsification agents and interface modifying substances having valuable uses in many industries, in each case im- 35 parting a property or function of a desirable character as will be in part disclosed hereinafter.

Considering the polyglycerol esters of my invention more in detail, such esters possess to varying degrees aflinity for oleaginous materials as well as'for water, aqueous solutions and aqueous materials in general. The aflinity for oleaginous materials is imparted to the esters principally by the presence of a lipophile acyl group or groups which impart to the molecule the tendency to dissolve or to disperse in oleaginous media; or at any rate a certain attraction for oleaginous materials. The hydroxy group or groups tend to impart'to these esters a capacity, to varying degrees, to dissolve or disperse in water 40 or aqueous media in general or at least to have a certain attraction for water and aqueous materials. On the relative potencies of the lipophile and hydrophile portions of a given molecule, the resultant activity of the molecule as a whole depends. These potencies are a function not only of the mass and number of groups constituting these relative portions of the molecules, but also on their structural orientation.

My polyglycerides may at will be'prepared to we be predominantly lipophile or predominantly hydrophile or balanced in the sense set out in great detail in U. S. Patents Nos. 1,917,250, 1,917,256, 1,917,249, and 1,917,257, in which event they manifest certain unique ,interfacial activi ties, such as the reduction of spattering of marphase of the relative characteristics and be-- havior of my esters.

A B c I o o mc-o-d-otnu mo-o-Hz-cm mo-o-g-ou,

In this set of examples, A is predominantly lipophile, C is predominantly hydrophile, and B" is intermediate and by virtue thereof possesses certain interfacial modifying properties not possessed at all by either A" or 0" or not to anything like the same extent they are manifested by B". C" is distinctly water soluble, A" is distinctly fat soluble, while B is intermediate. All three, however, by virtue of the fact that in each of the three molecules there is present both a lipophile and a hydrophile portion, have marked affinities for both oleagin'ous and aqueous media. Insofar as interface modification in relation to emulsification is concerned, those of my esters which are predominantly lipophile tend to favor the water-in-oil type ofemulsion, whereas those which are predominantly hydrophile tend to favor the oil-in-water type of emulsion.

The polyglycerol esters described in my copending application, Serial No. 697,533, above referred to, in general possess the characteristics and exhibit the functions touched on briefly in the preceding paragraphs. Since in general, the methods I employed in my prior application involve the re-esterification of an oil or fat with a polyglycerol, the resulting polyglycerol esters, generally speaking, also included a proportion of glycerol esters; The process and modifications thereof which I describe herein produce esters having a number of important advantages over those I have described heretofore'with respect to color, odor, taste and other desirable properties, and are further differentiated from my prior disclosed esters in that they are free of glycerol V a higher potency.

The esters I describe herein have free hydroxy Cgroups-at least one tree hydroxy group per molecule-which impart hydrophllic properties to a molecule which otherwise would be lipophile in character by virtue of the lipophile group or groups esterifled with the polyglyceroL, Many of my esters are potent antispatterers, others have wetting-out, penetrating and emulsifying properties, and all of them manifest activity at interfaces of varying degrees and in different manners, depending upon the character of the ester and the interface in question. All of them, however, are interface modifiers, particularly for interfaces between aqueous and oleaginous media, or between an aqueous medium and a solid with an adsorbed layer of oil, !at or other. oleaginous material.

My principal method for preparing these esters is to polymerize glycerol to a desired molecular magnitude, whether it be dlglycerol, triglycerol, tetraglycerol or higher polymerized glycerols or mixtures thereof, by heating glycerol by itself or in the presence of a catalyst, then freeing the polyglycerol or polyglycerol mixture of unpolymerized glycerol, if any be present, and finally esterifying the polyglycerol material, free of glycerol, with a fatty acid or a fattyacld mixture by reacting the two with or without the presence of an esteriflcation catalyst, or alternatively with acyl halides or acid anhydrides in or without the presence of a catalyst or condensing agent.

These three principal steps, as well as certain other ones, in the preparation 01' my esters, are described in the illustrative examples given here inbelow. V

The following examples, 1 to 6, describe the preparation of polyglycerol mixtures.

Example 1 500 pounds of chemically pure 94% glycerol, in which are dissolved 5 pounds of caustic soda, are heated at approximately 260C after initially boiling of! the original water content, for 4% hours with vigorous aspiration of C0: over the suriace at atmospheric pressure and with continuous mechanical stirring. The carbon dioxide gas minimizes oxidation, and assists in carrying of! moisture. Finally theproduct is cooled in an atmosphere of carbon dioxide. The resulting'polyglycerol product is a rather thick liquid of dark amber color and moderately caramelized a. odor and taste, with a mean molecular weight varying approximately between 148 and 163, whilethe molecular weight of an acyclic diglycerol is 166.

. Example 2 v 3 parts of flaked sodium hydroxide are'dissolved in 300 parts of 94% chemically pure glycerol. This solution is heated for nine hours under reflux in vacuo with a vigorous stream of nitrogen continually bubbling through the liquid. The nitrogen performs the function of stirring and assists in sweeping away water vapor. Heating ,is commenced, and after the initial moisture present has been boiled oil, the temperature of the mixture is raised to approximately 225 C. at a pressure of mm. These conditions are temperature and applying sufllcient vacuum by means of an evacuating jet, or a pump, so that despite the supply of nitrogen a desired pressure of 160 mm. of mercury is attained. As the nine hour heating period progresses, the temperature is gradually raised to 240 C. at an approximately uniform rate and the pressure is gradually lowered to 65 mm. also at an approximately even rate, so that at the end of the nine hours the conditions are approximately 240 C. at 65 mm. pressure. The temperature of the reflux con denser is adjusted to allow all moisture to escape and to cause glycerol to reflux back into the reaction mixture. The resulting polyglycerol product, when cooled to room temperature, is very thick, almost solid, extremely dark and strongly caramelized in odor and. taste. The mean. molecular weight of the product is 326, whereas an acyclic tetraglycerol is 314.

Example 3 sample 4 500 poundsof 94% c. r. glycerol with 5 pounds of caustic soda dissolved therein are heated in vacuum under reflux until the initial moisture content is substantially distilled out. The temperature is thenraised to 200 C. and the pressure adjusted to 127 mm. with C0: bubbling through the mixture. Heating is continued for eleven hours, the temperature being maintained approximately between 220 and 225 C., and the pressure gradually dropped at an approximately even rate from the initial pressure to 70 mm., C0: being continually bubbled through the mixture. Moisture, with small proportions of other materials, continues to escape, thereby giving a product, which, when cooled to room temperature, is an extremely viscous syrup of dark amber color but good odor and taste. Its mean molecular weight is 256, while the molecular weight of an acyclic triglycerol is 260.

Example 5 3 parts of caustic soda are dissolved in their own weight of water and the solution is then mixed with 300 parts of 94% glycerol, chemically pure grade. Nitrogen is bubbled through the mixture and heat and vacuum are applied, under reflux condenser, until the initial moisture is driven off. The temperature is then raised to 250 C. and heating under reflux with nitrogen bubbling through is continued for two and one quarter hours, manipulating the temperature' arm Example 6 400partsoiglycerolwith 4partsoffiakedcaustic soda dissolved therein are heated under vacuo with CO: continually bubbling through the mixture for two hours at a progremive of approximately 420 mm. to approximately 40 mm. of mercury, and a progressive temperature of approximately 250 to 260 C. (after boiling oi! the initial moisture present), the temperatures and pressures being progressively manipulated in the order described hereinabove. n cooling to room temperature, the product is seen to be a straw colored, very viscous syrup, practically free of all odor and taste. Its mean molecular weight is a 207.

While in the above examples, polymerization hasbeencarriedoutwiththeaidof causticsoda as a catalyst, it is possible to obtain polymerimtion without the use of catalysts, or when catalysts are employed, substances other than caustic soda maybe used; for example, sodium carbonate, sodium bicarbonate, other alkaline carbonates and hydron'des, calcium oxide, magnesium oxide, zinc oxide, trisodium phosphate, sodium tetraborate, sodium acetate and other alkaline and potentially alkaline materials, iodine, zinc chloride and the like. Furthermore, the proportion of caustic soda or other catalyst maybe varied.

In general, polymerization proceeds much more slowly and with greater difllculty without than with a catalyst. Much higher temperatures and considerably longer heatingperiods are required. Indeed, other things being equal, on the averageitmaytakethreetofourtimesaslong to reach a given degree of polymerization.

Example 7 illustrates a polymerization without a catalyst.

Example 7 500 parts of anhydrous glycerol are heated at atmospheric pressure for approximately fifteen hours with carbon dioxide bubbling through the liquid, from an initial temperature oi 265 to a final temperature of 305 C., the temperature beiug gradually raised as the time progresses. Moisture is allowed to escape whereas the glycarc] is substantially refluxed back into the mixture. The product is a practically odorless, straw colored liquid with a mean molecular weight of approximately 120. Although this reaction takes place at very high temperatures and for such a long period of time as fifteen hours, only about 30% of po y lycerols are formed, based upon the original starting material.

The following examples, 8 to .11, inclusive, indicate procedures for the treatment of polyglycerol mixtures to free them of unpolymerized glycerol.

Example 8 The polyglycerol mixture obtained in Example 1 is distilled in high vacuum under a pressure of about 2 mm. of mercury with a small stream of C0: bubbling through the liquid, the temperature of the liquid being maintained at about 220 to 225 C. lmtil no more glycerol comes oil, The product is a heavy, viscous syrup of dark amber color and caramelized odor.

Example 9 The polyglycerol mixture obtained in Example 3 is distilled in vacuum at a pressure of 2 to 5 mm. of mercury, the temperature of the liquid being gradually raised to approximately 235 C. and maintained at this point until no more glycerol distillsover. Aslowstreamofnitrogeniskegt circulating through the liquid during the distillation. The product, after cooling, is a viscous liquid with a straw color and 800d odor; in fact,

it is practically odorless. i

Example The polyglycerol mixture obtained in Example 5isdistilledinvacuum atapressureofamroxlmately 4 mm. of mercury, the temperature of the liquid being gradually raised to ap 250 to 255 0., and then maintained in this range until glycerol ceases to distill over. Distillation isstoppedatthispoint. 0ncooling,theproductisseentobeextrunelyviscous,almosta glass, at room temperature. Its color is light amber and it is practically odorless and Example 11 The polyglycerol mixture P pared as in Example'iisdistilled invacuumat mm. pressure and 240 C. until no more glycerol comes over. The residue of the distfllation is a viscous liquid mixture of polyglycerols with slightly caramelired odor and of S igh y darkened amber color.

Polye ycerol products may be treated-to modify or remove the catalyst present or they may be improved, especially as to their odor and taste, by various procedures, particularly by u at atmospheric pressure or under reduced pressure with saturated or superheated steam. An illustration of this kind of treatment is as follows:

Example 12 The polyglycerol mixture obtained in Exam fle 1 issteamdistilledatapresureofapprozximatelyto20mm.ofmercury andinatemperaturerange of to 200 C. for a period of, two hours, using approximately one part of steam by weight to one 'part of po yglycerol material. The resultant product is practically free of caramelized odor and taste. In othmrspects, it has the same properties as the product of Example 1. i I

In preparing the esters of polyglycerols, my preferred method is to heat the polyglycerol ma terial with a fatty acid or.a fatty acidmixture in a proportion insufilcient toesterify all of the hydroxy groups present, at atmospheric pres-' sures or super-atmospheric pressures, or in vacim or in vacuo under reflux, but in any case lmder conditions which permit the escape of the water formed during the reaction, and preferably imder conditions which are non-oxidizing.

Examples 13 to 17, inclusive, will serve to illus-- trate procedures for the preparation of my fatty acid esters.

Emmple 13 260 parts of the product prepared in Example 8, 141 parts of bleached and deodorized oleic acid and 141 parts of triple pressed saponiiied stearic acid are heated with stirring, in an atmosphere of CO: at 220 to 230 0., until the free fatty acid content of the-mixture is less than one-half of one percent. The duration of heating imder these conditions is approximately one and one- 1 half hours. Moisture is allowed to escape during the reaction. The product of this esteriiication is a mixture of polyglycerol esters with free hydroxy groups. It is light brown in color, free of objectionable odor and of a pasty consistency at room temperature, and has pronolmced antispattering power when added in of 7| approximately 1% or less to the usual margarine comprising cultured milk and oleaginous materials.

Example 14 450 parts of triple pressed stearic acid with a titer of about 56' C. are heated with 485 parts of the polyglycerol mixture prepared in Example 8. The mixture is stirred for two hours at from 220f to 230 C. by bubbling a stream of carbon dioxide through the liquid. The mixture is then .allowed to remain at rest and cooled in an atmosphere of, CO2. A small amount of pureacted polyglycerol settles out and is separated from the, esters. The esters show a free fatty acid content of 3%, are free of undesirable odors and taste and have a pale buifcolor after being allowed to solidify and coolto room temperature. The-product is friable, but not very hard, and is very potent with regard to the reduction of spattering of margarine during frying.

, Emmple 15 500 parts of the product'obtained in Example l4 and 260 parts of triple pressed stearic acid are heated with stirring, in a non-oxidizing atmosphere at a temperature of approximately 240 to 250 C. for two and one-quarter hours, the moisture of the reaction being permitted to escape. The product is a brittle buff colored solid with a free fatty acid content of approximately one-half of one percent.

Example 16 esters with free hydroxy groups,of good color,

odor and taste, with a free fatty'acid content of about 3%, and withmarked antispatteringpower.

/ Example 17 90 parts of the polyglycerol mixture prepared as in Example 11, are heated with 145 parts of United States Pharmacopoeia oleic acid of good color and odor, at approximately 225 C. with a vigorous stream of carbon dioxide bubbling through the mixture until ,the product shows less than V: of 1% of free fatty acid. This condition is reached in approximately one and one-half hours. The reaction mixture is allowed to cool in a stream of carbon dioxide. The product is a very heavy viscous liquid mixture ofpolyglycerol esters with free hydroxy groups. Its color is light brown and it has marked hydrophilic properties, with considerable power to reduce the spattering of margarine during frying.

, f the above examples, 13 to 17, it will be noted that in Example approximately two molecules of fatty acids on the average have been esterifled with one molecule of polyglycerol, whereas in the other examples on the average only one molecule of fatty acid has been esterifled with one molecule of polyglycerol. This ratio may be even further varied, depending upon the product desired. In all cases, useful esters will be obtained as long as at least one hydroxy group remains unesterii'led.

In addition to the fatty acids employed in Examples 13 to 17, other mono-basic acids of edible use:

or inedible, technical grade, may be employed to give useful hydrophilic esters of po yt ycerols.

Either single organic acids or mixtures of carboxylic or sulphonic acids may be employed. Any of the fatty acids obtainable by saponiilcation or hydrolysis of animal or vegetable oils, fats or waxes, or hydrogenation products thereof, are suitable for the purposes of my invention. Examples of single fatty acids are acetic, propionic, butyric, valeric, caprylic, caproic, capric, lauric, myristic, palmitic, stearic, oieic, ricinoleic, hydroxystearic, behenic, linoleic,linolenic, naphthenic acids, benzenesulphonic, naphthalene-sulphonic, and other aromatic sulphonic acids, cetylsulphonic, dodecylsulphonic, benzoic acid, naphthoic acid, and other aromatic mono-carboxylic acids, etc. Examples of oils and fats and other materials from which satisfactory mixtures of the carboxylic acids may be derived are as follows: coconut, palm kernel, tallow, oleo oil, oleostearine, cottonseed, palm, soy, corn, sunflower, sesame, linseed, whale, fish oils, lard, rosin, and hydrogenation products thereof.

In instances where my polyglycerol esters are to be employed for food purposes, as for example in improving an oleomargarine or a shortening or a cake batter, I employ fatty acid materials and glycerol of food grade. In other cases, where the ester is to be used for technical or industrial purposes, lower grades of fatty acid materials and cheaper grades of glycerol may be employed.

While my present invention includes the preparation of relatively pure sub'stanceshaving decided advantages for certain purposes, it should be remembered that for many purposes, mixtures are more potent and produce better results than the relatively pure substances. For this reason, I prefer often to use a mixtureof fatty acids for esterification withthe polyglycerols rather than a relative pure fatty acid product such as stearic acid, for example. Mixed fatty acids derived from many of the ordinary oils and fats can, therefore, be used with very good results, in many cases. In any case, my present substance may be made free of glycerides. Thesesubstances also are free of glycerine, and therefore have a much lower smoking point than substances including small amounts of glycerine.

In general, my polyglycerol esters, with respect to their consistency and other purely physical characteristics, are parallel to the fatty acids or mixture of fatty acids from which they are prepared; that is to say, a polyglycercl ester made from a liquid fatty acid is normally liquid at room temperature, one made from a solid fatty acid or mixture of solid fatty acids is solid at room temperature. This does not mean, however, that the Physical characteristics of the esters are identical with those of the acids from which they are prepared. In fact, in general the ester is somewhat softer ln the case of solid ones, and in the case of liquid ones somewhat more viscous and syrupy than the liquid fatty acids from which they are prepared. The colors. of my esters depend largely on the color of the poiyglycerol mixture,,in the sense that a dark colored polyglycerol mixture will produce a dark colored ester, irrespective of how good the color of the fatty material may be. It is, therefore, advantageous in general to use polyglycerol products of good color, methods for the preparation of which have been fully described herein.

Some of the improvements in the methods I employ in accordance with my present applica- 7' tion result from the improved manner of prepar- 12. The method of producing an interface modiing the initial polyglycerols. Inasmuch as many fying agent in the form of an ester of polyerols are new, my invention is also directed to hydroxy grou which comprises polymerizing 5 the sub-combination of steps involved in preparglycerine, heating the polymerized product 5 ing the polyglycerols. under reduced pressure to distill on unreacted What I claim as new and desire to protect by glycerine,v and esterifying the glycerine free Reissue Letters Patent of the United States is: product with a mixture of fatty acids.

1. An interface modifying agent comprising an 13. An interface modifying agent, having a 10 ester 01' polyglycerol and a relatively high moliquid to plastic consistency at room temperature. 9

2. An interface modifying agent comprising gly rol hydroxy group. esters of mixed po y ycerois and a relatively 14. An, interface modifying agent, having a high molecular weight monobasic aliphatic or-] liquid to plastic consistency at room temperahydroxy group; a 15. An interface modifying agent. having a 4. An interface modifying agent comprising an liquid to plastic consistency at room temperaesters of mixed polyglycerols and a relatively 16. Interface modifying agents in the form of so 6. An interface modifying agent comprising 17. An interface modifying agent comprising esters of mixed polyglyoerols and mixed relativean ester of a polyglycerol and a monobaslc alily high molecular weight mono-basic aliphatic phatic acid containing more than 18 carbon carboxylic acids, said esters having at least one atoms, said ester having at least one free polyoxy group. glycerol hydroxy group. 7.'An interface modifying agent in the form of 18. The method of producing interface modifypressure to distill of! unreacted glycerine, and presence of an alkaline reacting catalyst to pro- 00