US1917258A - Emulsion - Google Patents

Description

260. CHEMISTRY, CARBON COMPOUNDS rarented July 11, 1933 UNITED STATES BENJAMDQ' R. HARRIS,

EMULSION No Drawing. Application filed September No. 475,622, filed August 15, 1930,-as a con-- tinuation in part of application Serial No. 383,143, filed August 2, 1929.

Those skilled in the art are referred to my co-pendin application, SerialNumber 566,156, filed September 30, 1931 as a'continuation in part of application Serial No.

475,622. In general the present invention represents a specific embodiment of the main invention disclosed in the (Io-pending application above referred to, and while the present disclosure is substantially complete in so far as it describes the'invention and supports the claims, those interested inthe art are referred to the co-pending case for a more com plete disclosure of the basic concept of theinvention.

The principal object of my present invention is to improve'such forms of emulsions as margarine.

Another object is to reduce the spattering of margarine when used forfrying purposes and generally improve its frying behavior.

Other objects and features of the invention will be apparent from a consideration of the following detailed description. f

As was disclosed in my prior applications I have discovered a large class of chemical compounds which may be used to im art improved characteristics to all types 0 wateroil emulsions, particularly those used for cooking purposes, and other types of culinary fat-preparations. These substances have several characteristics in common which make them ver valuable in their use with margarine. These substances are compatible with mild acids and in particular with lactic acid in the concentration and under the conditions existing in margarine. In general they are difiicultly soluble in oils and fats and aqueous media and in many cases are substan- PATENT OFFICE OF CHICAGO, ILLINOIS 30, 1931. Serial No.566,158.

.use most.of these compounds in very small quantities, as they may be considered to concentrate at the water-oil interface of the emulsion rather than be freely dissolved in either the water or oil phase. These sub stances are semi-colloidal or truly colloidal in character and are frequently colloidally dispersible' .in aqueous and/or oleaginous media. They are, moreover, substantially non-volatile at margarine frying tempera-' tures and so will remain in the margarine and perform.their'funct.ion during frying.

. One of the most important characteristics of these'compounds is the presence in the molecule of two t pes of groups in balanced relation to each ot er,-one group being hydrophyllic and water wetting in character, and the other group being lipophyllic and fat wetting in character. These groups must exist in the molecule in such a state of balance that they will function at the water-oil interface in the intended manner. Presumably these substances orientate themselves at the water-oil interface, by reason of the balance of the two typesof groups, but it is understood that the invention does not depend upon this explanation.

My prior application treats exhaustivelyof the manner in which the balance between the two groups may be determined so that without tests of any kind it is possible for the skilled colloid chemist to pick'out compounds which can not function effectively as antispatterers, as well as compounds which clearly will be effective as anti-spatterers.

However, there are compounds of. such character that the "state of balance existing between the two groups in the molecule is preferably determined by a simple quick test The balance of the hydroph'ile-lipophile groups in the compound which I apply in my invention is one of the characteristics and determinants of the class of substances which I employ.

The test which I have chosen as a means for, determiping the hydrophile-lipophile balance in organic compounds, I call the spoon test. his carried out as follows:

50 tially insoluble. This makes it possible to From 0.05 to 0.20 gr. of the material or sub- 260. CHEMISTRY, CARBON COMPOUNDS.

stance in question is introduced into a porcelain mortar, wetted and grouml into a smooth paste with a pestle or dissolved with a minimum proportion of water; two to five drops generally will suffice.

An ordinary margarine such -for example as one made from vegetable oils, and fats and cultured skimmed milk and which possesses the usual property of spattering during frying is selected. Ten grams of this margarine are then introduced in small portions into the mortar and macerated thoroughly with the paste first prepared until the entire ten gram portion is thoroughly and uniformly intermixed with the material in the mortar.

Two grams of this mixture are introducedinto a tablespoon and held directly over a free flame, such as for example a Bunsen flame, one or two inches long, in such a position that the point of the flame just about reaches the bottom of the spoon. A clean sheet of paper is placed on the bottom of the burner by inserting the stem of the Bunsen burner prior to lighting through a hole made in the center of the paper and allowing the paper to drop to the base of the burner to catch the margarine splashed out during the heating. The mixture in the spoon is heated until all the water is boiled off and ebullition ceases and the spots on the paper I observed.

If this treated margarine spots the paper to the same extent as the untreated margarine from which the former was prepared, then the lipophile and hydrophile groups of the compound are not balanced. The number and size of spots on the paper or the added weight can be readily determined.

If the increase in weight of the paper or the number and character of the spots produced on the paper up until all the water has boiled oil are less than that produced by similarly heating two grams of the original untreated margarine employed for the test, then the material or substance in question has balanced hydrophile-lipophile groups. The expression balanced lipophile and hydrophile groups used in the claims is to e interpreted in terms of the above described spoon test, and in the light of the entire disclosure.

As will appear from my co-pending applications, it is not as a general rule. advisable to employ nitrogenous compounds as antispatterers, even though their anti-spattering behavior-may be very satisfactory. This is dueto the fact that many nitrogenous compounds are very apt to liberate from themselves, when used in margarine and other types of emulsions, objectionable substances such as choline or other objectionable amines. I state for this reason in the co-pending application above set out, that I prefer to avoid the use of nitrogenous compounds. I have dlscoi 'ered, however, that many nitrogenous compounds can be used with satisfaction providing the nitrogenous compounds selected are of such a character that no objectionable taste and odor can in any way be develo ed during conditions incident to the manu acture, storage, and use of margarine. I have found that if the molecular structure is devoid of the nitrogenous linkage o o CxsHu-(J-Ih-CHz--OH Stearyl creatinine, (sodium salt) Stearyl glutamic acid,

Cholesteryl ester of betaine chloride,

-Melissyl dimethyl-aminoacetate hydro bromide,

I O CH3 CH1" CaHgr-O-ll-CHQ --HB1 Pahnityl ester of betaine chloride v Cholesteryl ester of betaine bromide (Carbopalmitoxy) methyl pyridynium bromide,

Mellissylester of betaine bromide Mellissyl ester of'betaine chloride (Carbocholesteroxy) methyl pyridynium bromide. v

(Carbocholesteroxy) methyl dimethylphenyl-aminonium bromide I CgHrO-El-CHrN HaC $1: (Carbocholesteroxy) methyl quinaldilium bromide CHI Br Cholesteryl dimethyl-aminoacetate hydrobromide 0 on. on; C H45O'-illcH: 1q-BI Palmityl ester of dimethylaminoacetic acid hydrobromide 0 CH: CuHu0!1-CHr-Il-H Br on;

It will be noted that in every case, the antiwtrogenous hydrophile groupsas well as lipophile groups, but which nevertheless, are not anti-spatters are as follows:

aussian In the above listed examples, the hydrophile group dominates and is inadequately balanced by the l ipophile group, that is, the lipophile characteristics of the latter are too weak to adequately balance and coact with the hydrophile group, and for this reason anti-spattering power is lacking. This matter is more fully discussed in my co-pending: application, Serial No. 566,156.

A general method for the preparation of the anti-spattering agents w1th which the present application is concernedis to dissolve mixture protected from contact with atmospheric moisture, is then allow-ed to stand at room temperature or is agitated at room temperature for six or eight hours or longer, and is then poured into iced dilute Sill-- phuric acid, or some other acidulating agent. The product generally separates out, in the case of the acyl chloride of solid fatty acids, as flocculent solid, and in cases where acyl chlorides of liquid fatty acids have been used, generally speaking, as a liquid or semi liquid material.

It may then be washedseveral times with water or with brine, at room temperature or with the application of heat and finally separated from the Water and dried.

In this procedure other basic materials such as dimethyl aniline, quinoline, or quinaldine may be substituted for the pyridine. Also, the acylation may be carried out in a different anhydrous medium or in an aqueous medium using a basic material such as calcium hydroxide or carbonate to take care of the hydrochloric acid formed during the course of the reaction.

The products may be purified, if desired, by recrystallizing from solvents.

Some of the anti-spatterers of the class described herein which I prepared by the pyridine method are listed hereinbelow, with the proportions of the reacting materials used, indicated. The comparative anti-spattering powers of the fatty acid derivatives thus'obtained are also shown. These antispatterin powers were determined by the method escribed herein and in my co-pending application.

1 part glycine 1 part creatmine.

2 parts glutem acid.

c on e. 4 pts. stearyl chloride.

50 parts pyridine 45 pts. pyridine 55 pts. pyridine pts. pyridine 60 pts. pyridine Fair.

Moderate (sodium salt) Very good.

Good.

Very good.

1 do not, of course, limit my invention to the products obtained by using the above listed reagents in the proportions indicated,

nor do I even limit my invention to products obtained by the above described method, however, the proportions of the reagents may have been varied.

The scope of my invention includes compounds, however prepared, when such compounds comprise lipophile and hydrophile groups and when the hydrophile group contains nitrogen, in a linkage other than OX-O-(CH N- as herein described. Many other nitrogenous materials than those mentioned may be utilized to furnish the hydrophile function, for example,

260. CHEMISTRY, CARBON IOMPOUNDS.

alanine, phenylalanine, tyrosine, tryptophane, arginine, other amino acids, and other nitrogenous substances with marked aflinity for water.

Many other materials than those mentioned may be utilized as sources of lipophile groups, for example: melissic acid, oleic acid, lauric acid, lauryl alcohol, palmityl alcohol, hi her molecular weight esters and other mistances with marked affinity for oils and fats, as pointed out more fully in my copending application, Serial No. 566,156.

I may, for example, hydrolize a protein down to the amino acid stage by the use of a strong mineral acid or otherwise, then neutralize and dry the mixture and acetylate more or less by the general method describedherein with the acyl chloride of a higher molecular weight fatty acid.

There are also many special methods available. Stearyl glycine, for example, may be prepared by heating together stearamide with chloracetic acid or with sodium chloracetate.

The nitrogenous substances of my invention may be represented by the formula e f and fO a ca bonand o ygen 0 CHa-(CHzhrEl-R wherein R represents an amino acid radical devoid of the objectionable linkage referred to. With reference to the betaine series, I may express my formula asfoflowsz o on, i

O I CHg-CHz-CHz-CHg- CH:CH:CH: CH:- O- iL- CHg-N Among the preferable compounds are also the peptones acylated with fatty acids of higher molecular weight, such as stearyl peptone, for example.

While I have not set forth in detail the compounds shown in the tables are covered 79 by such formula, together with additional compounds not disclosed which may be pro- 7 duced in accordance with the invention and function satisfactorily as anti-spatterers. It

is to be noted that in each chemical substance noted hereinabove to have balanced groups and reduce spatter-ing in margarine, the hydrophyllic group is at or near anend of the molecule. This position undoubtedly affects the power of the molecule readily to orientate 80 itself at the Water-oil interface.

It must not be inferred from the preceding part of this specification that every anti spatter-ing substance of the character herein disclosed must be. insoluble in oleaginous 35 and/or aqueous media. It is true that the greater number of anti-spattering com- ,series, there. is apointor. rangeatavh-ich-lip- 7 pounds of the present invention are substantially insoluble in these media, but there are a limited number of water soluble compounds which, if used in suiiiciently lar er proportions, may have an effect in reducing spattermg during-frying.

Itappears that in a given. homologous ophile and hydrophile characteristics are so balanced that an optimum power for the prevention of spatter-ing is imparted to the molecule. Going from this point higher in the series, in the direction of the increasing molecular weight in the lipophile group with a given nitrogen containing radical in the hydrophile group, the anti-spattering power diminishes, because of excessive lipophile characteristics in the molecule; going down from this point or range lower-in the series, anti-spattering power again diminishes, because of the excessive hydrophile characteristics iii-the molecule; the tendency to dis- I l solve in water concurrently increases. In certain homologous series, however, there are cases of water soluble substances which can function as anti-spatterers'. Examples of water soluble nitrogenous compounds which may be used as a'nti-spatterers are C fla/ m able anti-spatterers not soluble in water is Search Room greater than the number of soluble ones. This is apparent from the following consideration. Generally water solubility is negligible in anti-spatterers with a relatively large number of carbons in the lipophile group. As the number of carbons in the lipophile is decreased, however, toward the lower end of the series, water solubility gradually increases, until finally the compounds become so prevailingly hydrophyllic that anti-spat tering power is absent. In general, therefore, the total number of water'soluble anti-spattering compounds is relatively small.

As to the specific application of the invention to margarine or other emulsions and oleaginous culinary emulsions, it is clear that there are many nitrogenous compounds devoid of the linkage described containing balanced hydrophile and lipophile 'groups. It is impractical and unnecessary to list each particular combination which can be used in accordance with my invention. Moreover, while I leave something to the skill of persons applying my invention, the description is sufiiciently exhaustive, particularly when considered with respect to the prior applications, to enable those skilled in the art successfully to practice the same.

The term non-spattering margarine as used in the claims is employed to designate a margarine, the frying behavior of which is improved by the addition thereto of the novel materials of my invention herein described, to reduce spattering. The term margarine includes all forms of margarine type of emulsions intended for culinary and table use, either containing animal or vegetable fats, and either churned with cultured milk, sweet milk, water or other types of oleaginous material.

I claim:

1. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a nitrogenous emulsion improver represented by the formula wherein C and O are carbon and oxygen,

respeetively, L is the lipophile radical in the form of an alkyl or alkoxy group, or a. derivative of an alkyl or alkoxy group and R represents a balancing nitrogenous hydrophile group devoid of the linkage wherein 0 represents oxygen; X stands v for phosphorus or sulphur in the form of oleaginous phase and an aqueous phase, and

having included therein a proportion ofv a nitrogenous emulsion improver represented by the formula L( iR wherein C and O are carbon and oxygen, respectively, L is the lipophile radical in the form of an alkyl group of higher molecular weight and R represents a balancing nitrogenous hydrophile group devoid of the linkage OXO CH w "N- wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form of their oxygenated acid radicals; C represents carbon; H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

3. A non-spattering margarine having an oleaginous base and an aqueous phase, and having inc uded therein a proportion of a nitrogenous emulsion improver represented by the formula 0 onriongrd-n wherein R represents a balancing nitrog enous hydrophile group devoid of the link age wherein 0 represents oxygen; X stands for phosphorus-or sulphur 1n the form of .their oxygenated acid radicals; C represents carbon; H is hydrogen; w is a wherein R represents a balancing amino acid radicaldevoid of the linkage wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form of their oxygenated acid radicals: C represents carbon; H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

5. A non-spatteringmargarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of stearyl glutamic acid.

6. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a ace nitrogenous emulsion improver represented by the formula wherein C and O are carbon and oxygen, respectively, L is a lipophile group and R is a balancing betaine radical devoid of the linkage wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form of, their oxygenated acid radicals; C represents carbon; H is hydrogen; 'w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

7. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a nitrogenous emulsion improver represented by the formula C, 077, H, N O1 repre sent carbon, oxygen, hydrogen, nitrogen, and chlorine respectively and L is a balancing lipophile group.

8. A nofispattering margarine having an oleaginous phase and an aqueous phase, and having included therein palmityl betai-ne chloride.

9. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of an improver including peptone combined with a balancing fatty acid of higher molecular weight.

10. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of stearyl peptone having balanced lipophile and hydrophile groups.

11. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a nitrogenous emulsion improver represented by the formula I? LCR wherein C and O are carbon and oxygen, respectively, L is the lipophile radical in the form of an alkyl or alkoxy group, or a derivative of an alkyl or alkoxy group and R represents a balancing nitrogenous hydrophile group devoid of the linkage -o x o- (CH N wherein 0 represents oxygen: X stands for phosphorus'or sulphur in the form of their oxygenated acid radicals; C represents carbon; H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon, said compound being sparingly soluble in aqueous and/or olcaginous media.

12. A non-spattering margarine having an oleaginous phase and an aqueous phase, and having included therein a proportion of a water soluble nitrogenous emulsion improver represented by the formula wherein C and O are carbon and oxygen, respectively, L is the lipophile radical in the form of an alkyl or alkoxy group, or a derivative of an alkyl or alkoxy group with at least eight carbons, and R represents a balancing nitrogenous hydrophile group devoid of the linkage wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form of their oxygenated acid radicals; G represents carhon; H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

An emulsion comprising an oleaginous phase, an aqueous phase, and a proportion of a nitrogenous emulsion improver represented by the formula but not including stearamid, wherein C and O are carbon and oxygen, respectively, L is the lipophile radical in the form of analkyl or alkoxy group, or a non-aromatic derivative of an alkyl or alkoxy group and R represents a balancing nitrogenous hydrophile group devoid of the linkage wherein 0- represents oxygen, X stands for phosphorus or sulphur in the form of their oxygenated acid radicals; C represents carbon: H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

14. An emulsion comprising an oleaginous phase, an aqueous phase, and a proportion of a nitrogenous emulsion improver represented by the formula but not including stearamid, wherein C and O are carbon and oxygen, respectively, L is the lipophile radical in the form of an alkyl group of higher molecular weight DGQTCH HUUH] and R represents a balancing nitrogenous hydrophile group devoid of the linkage wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form of their oxygenated acid radicals; C represents carbon; H is hydrogen; w is a small whole number and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

15. An emulsion comprising an oleaginous phase, an aqueous phase, and a proportion of a nitrogenous emulsion improver represented by the formula but not including stearamid, wherein R represents a balancing nitrogenous hydrophile group devoid of the linkage wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form-of their oxygenated acid radicals; C represents carbon; H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to carbon.

16. An emulsion comprising'an oleaginous phase, an aqueous phase, and a proportion of a nitrogenous emulsion improver represented by the formula but not including stearamid, wherein R represents a balancing amino acid radical devoid of the linkage wherein O represents oxygen; X stands for phosphorus or sulphur in the form of wherein C and O are carbon and oxyen, respectively, L is a non-aromatic ipophile group and R is a balancing betaine radical devoid of the linkage wherein 0 represents oxygen; X stands for phosphorus or sulphur in the form of their-oxygenated 'acid radicals; C represents carbon; H is hydrogen; w is a small whole number; and N is trivalent or pentavalent nitrogen, the terminal oxygen indicated being directly linked to car- 19. An emulsion comprising an oleaginous phase, an aqueous phase, and a proportion of a nitrogenous emulsion improver represented by the formula m L-O-E-CHr-IbF-Cflsom 1 h ei C, O, H, N and C1 rep resent carbon, oxygen, hydrogen, nitrogen, and chlorine respectively and L is a balancing non-aromatic lipophile group.

In witness whereof, I hereunto subscribe my namethis 26 day of Sept, 1931.

BENJAMIN R. HARRIS.