US2347178A - Reversible emulsion and application therefor - Google Patents
Reversible emulsion and application therefor Download PDFInfo
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- US2347178A US2347178A US425856A US42585642A US2347178A US 2347178 A US2347178 A US 2347178A US 425856 A US425856 A US 425856A US 42585642 A US42585642 A US 42585642A US 2347178 A US2347178 A US 2347178A
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- oil
- water
- acid
- emulsion
- emulsions
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- 239000000839 emulsion Substances 0.000 title description 47
- 230000002441 reversible effect Effects 0.000 title description 14
- 239000003921 oil Substances 0.000 description 51
- 235000019198 oils Nutrition 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 15
- 230000001804 emulsifying effect Effects 0.000 description 13
- 239000004615 ingredient Substances 0.000 description 13
- -1 amino compound Chemical class 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 9
- 239000006260 foam Substances 0.000 description 9
- 244000068988 Glycine max Species 0.000 description 8
- 235000010469 Glycine max Nutrition 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- 240000007594 Oryza sativa Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 235000019483 Peanut oil Nutrition 0.000 description 2
- 235000005687 corn oil Nutrition 0.000 description 2
- 239000002285 corn oil Substances 0.000 description 2
- 235000012343 cottonseed oil Nutrition 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 235000019197 fats Nutrition 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- 239000000312 peanut oil Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- MXBCYQUALCBQIJ-RYVPXURESA-N (8s,9s,10r,13s,14s,17r)-13-ethyl-17-ethynyl-11-methylidene-1,2,3,6,7,8,9,10,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-ol;(8r,9s,13s,14s,17r)-17-ethynyl-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthrene-3,17-diol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C1CC[C@@H]2[C@H]3C(=C)C[C@](CC)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 MXBCYQUALCBQIJ-RYVPXURESA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- ILGDHIVXCCAQET-UHFFFAOYSA-N C(CN(C=C)C=C)N(C=C)C=C.C(C)O Chemical group C(CN(C=C)C=C)N(C=C)C=C.C(C)O ILGDHIVXCCAQET-UHFFFAOYSA-N 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 241001446467 Mama Species 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021319 Palmitoleic acid Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000010495 camellia oil Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SECPZKHBENQXJG-UHFFFAOYSA-N cis-palmitoleic acid Natural products CCCCCCC=CCCCCCCCC(O)=O SECPZKHBENQXJG-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 125000005313 fatty acid group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000021323 fish oil Nutrition 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- MJCJUDJQDGGKOX-UHFFFAOYSA-N n-dodecyldodecan-1-amine Chemical compound CCCCCCCCCCCCNCCCCCCCCCCCC MJCJUDJQDGGKOX-UHFFFAOYSA-N 0.000 description 1
- 239000010697 neat foot oil Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/40—Mixing liquids with liquids; Emulsifying
- B01F23/41—Emulsifying
- B01F23/414—Emulsifying characterised by the internal structure of the emulsion
- B01F23/4142—Inversed-type emulsions
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/22—Amides or hydrazides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/07—Organic amine, amide, or n-base containing
Definitions
- n. N. 1.. a corpora This invention relates to, emulsions of waterin-oil, oil-in-water and intermediate types, and
- Another object is to provide a water-in-oil emulsion which can' be added to a batch or stream of aqueous stock in process to obtain the effect of adding an oil, without, however, encountering any subsequent difiiculties due to separation of the oil from the stock.
- a further object is to provide an agent and process for defoaming aqueous stock which will require only a minimum quantity of material and 'which will not interfere with any subsequent operations upon the stock.
- the amide of oleic acid with ethylene diamine was cited as a suitable emulsifying agent for the practice of this invention, but any fatty compound having at one end a fatty residue of 10 or more carbon atoms and no hydrophilic groups, and presenting at the other extremity an amine group, will be suitable. Examples of such compounds are fatty amines and the amides of the fatty acids with the'polyamines.
- an acid residue'in such an amide there may be cited oleic acid, lauric acid, myristic acid, palmitic acid, stearlc acid, palmitoleic acid,'arachidic acid and the like.
- the fatty acid residues contained in fats and oils such as coconut oil, soyabean oil, lard, tallow, peanut oil, corn oil, hydrogenated soyabean oil, hydrogenated fish oil, and the like may be employed.
- the amide residue may be derived from an? polyamine such as ethylene diamine, diet-hylene triamine, ethanol ethylene diamine, tetraethylene pentamine, 1,3 diamino isopropanol and the like.
- amides coming within the above requirements are exemplified in the amide produced by reacting oleic acid and ethylene diamine; rice oil with diethylene triamine; soyabean oil with diethylene triamine, hydrogenated soyabean oil
- suitable amines are stearyl amine, oleyl amine, lauryl amine, dilauryl amine, and the like.
- Acetic acid was cited as a suitable acid for adjusting the pH of the cationic surface active amino compound.
- any acid may be used for this purpose, preferably a weak acid, in order that the pH may be adjusted more accurately and that a buffering action may be secured.
- a suiiicient amount of the acid is employed to reduce the pH ofthe amino compound to 6 or below when the amino compound is in 2% aqueous solution.
- Petroleum oil was cited as an oil suitable -for theoily phase of emulsions according to this invention.
- any mineral, vegetable or animal oil, fat or wax may be employed.
- Mineral oils may vary in viscosity from about 35 seconds to 300 seconds Saybolt (100 F.)
- Suitable oils, other than mineral oils are exemplified in soyabean oil, cottonseed oil, rice oil, peanut oil. corn oil, teaseed oil, neats-foot oil, cod oil, castor oil, whale.
- the diluted and inverted emulsions have the propertiesunlike those'of most oil-in-water emulsions, in that they have a greasy feel and a tendency to prevent and destroy foam on any aqueous bodies containing them.
- these emulsions when added to any batch or stream of materials in" process, they will exert the same action as an unemulsified oil would, with the advantages that-a considerably less amount of actual oil is used, since the bulk of the emulsion will be constituted of water, and further, that the emulsion will subsequently disperse complete ly in the stock without separating and interfering at subsequent points in the process.
- the emulsions may be added to paper or glue stocks at.any point where foaming is encountered and will kill the foam at that point.
- the oil will eventually becom distributed thoroughly throughout the body of the stock and will not cause troubles such as, in the case of the paper, streaks in the paper web made therefrom, or in the case of glue, fish eyes on the coatings made therefrom. Further, these emulsions will not readily attack the rubber or other oil-sensitive materials contacted by the stock to which they are added.
- Example I 270 parts of #2 fuel oil, parts of the monoamide produced by reacting oleic acid with ethylene diamine, and 1 part of glacial acetic acid were mixed. 300 parts of water were added and mixed in with agitation to form. an emulsion of .water in oil. 200 additional parts of water were without breaking.
- Example 11 270 parts of #2 fuel oil, 80 parts of the monoamide produced by the reaction of hydrogenated soyabean oil with ethanolethylene diamine, and 1 part of gracial acetic acid were mixed. 300 parts of water were added and mixed in with agitation to form an emulsion of water in oil. This emulsion exhibited the same capability of inversion The foam broke down Example I. The emulsion of this example had excellent defoaming properties.
- Example III 30 parts of the monoamides formed by react.- ing a mixture of rice oil and cottonseed oil with diethylene triamine were substituted for the 'monoamides employed in the procedures of .Ex-
- Example IV The procedures of Examples I and II were repeated, using stearylamine in place of the mono sions which are readily inverted by mere dilu- 'tion and slight agitation. When such inversion occurs as the emulsions are added to aqueous,
- a reversible emulsion of water in oil the active emulsifying ingredient of which comprises chiefly a cationic surface acitve fatty amino compound, the fatty residue of which contains at least 10 carbonatoms and no hydrophilic groups, the amino compound being adjusted with acid to have a pH of about 6.0 cries in 2% aqueous solution.
- a reversible emulsion of water in oil the active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting oleic acid and ethylene diamine, the monoamide being adjusted with acid to have a pH ofabout 6.0 or less in 2%. aqueous solution.
- active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting hydrog'e'nated soyabean oil with ethanol ethylene diamine, the monoamide being adjusted with acid to have a pH of about 6.0 or less in. 2% aqueous solution.
- a reversible emulsion of'water in oil the active emulsifying ingredient of which comprises chiefly a fatty amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
- the amino compound . being adjusted by means of acetic acid to have a pH of in 2% aqueous solution.
- a reversible emulsion of water in oil the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amidoamine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amido-amine being adjusted by means of acetic acid to have apH of about 6.0 or less in 2% aqueous solution.
- a reversible emulsion of w ater in oil the active emulsifying ingredient of which comprises about 6.0 or less chiefly the monoamide formed by reacting oleic,
- the monoamide being acfiusted by means of acetic acid to have 'a pH of about 6.0 or less in 2% aqueous solution.
- a reversible emulsion of water in oil the' active emulsifying ingredient of which comprises chiefly a fatty amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amine being adjusted by means of acetic acid to have a pH of about 6.0 or less in 2% aqueous solution.
- a defoaming agent comprising oil, water and an emulsifying agent which compriseschiefly.
- amidoamine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
- Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amino compound,
- the fattyresidue of which contains at least 10 carbon atoms and no hydrophilic groups the amino compound being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
- Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amide-amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amido amine compound being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
- Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting hydrogenated soyabean oil with ethanol ethylene diamine, the amide being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
- Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly 15.
- Method of suppressing foamin aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly stearylamine, the stearylamine being adjusted with acid to have a. pH of about 6.0 or less in 2% aqueous solution, I JAMES H. FRITZ.
Description
mama Apr. 35,1944
w ns navna'smnn nnnmsrou sun armresrrou n a James H. ri-uz, swim; and Edwin L. abunson, Ghatham, N. 1., assignors to National Oil lroductscompanyJlai-rlso tion of New Jersey lilo Drawing.
Application January Serial No. 425,856
n. N. 1.. a corpora This invention relates to, emulsions of waterin-oil, oil-in-water and intermediate types, and
more particularly'to such emulsions which are stablized by means of cationic surface active amino compounds.
. Heretofore emulsions of water in oil have been prepared which are convertible by dilution and vigorous agitation to emulsions of oil in water, However, it has not been possible to prepare emulsions of water in oil which are stable at or near the inversion point or which may be converted by very mild agitation and dilution to oilin-water emulsions, notwithstanding the considerable'need for such stable and readily invertible emulsions.
Accordingly, it is an object of this invention to provide water-in-oil emulsions which can be readily and smoothly inverted and which will be stable at or near the inversion point.
Another object is to provide a water-in-oil emulsion which can' be added to a batch or stream of aqueous stock in process to obtain the effect of adding an oil, without, however, encountering any subsequent difiiculties due to separation of the oil from the stock.
A further object is to provide an agent and process for defoaming aqueous stock which will require only a minimum quantity of material and 'which will not interfere with any subsequent operations upon the stock.
The above and other objects are secured by this invention in an emulsion of an oily material, such as a petroleum oil and water, stabilized by a cationic surfaeeactivefatty amino compound,
such as the amide produced by reacting oleic acid with diethylene triamine, which compound is adjusted by means of a weak acid, such as acetic acid, to a pH of 6 or below. At moderate concentration of the oil, the oil will be the continuous phase,but upon dilution with water the emulsion inverts to'become an oil-in-water emulsion. Both the undiluted and diluted emulsions areentirely stable at any point in the process of inversion, which will take place without the rial eventually disperse throughout the stock without separating. Specifically, it is often desired to break the foam on the surface of Paper stock, glue, starch, casein solutions undergoing .ill
. with ethanol ethylene diamine, etc.
use of these emulsions for many applications, as V where it is desired to treat an aqueous stock with an oily material and to have the oily mateenzymatic and hydrolytic processes and the like, by adding an oily material threto. The emulsions of this invention will act as such an oil. but will eventually disperse smoothly and com- -pletely throughout thebody of the stock and thus avoid interference with any subsequent operations. 7
The amide of oleic acid with ethylene diamine was cited as a suitable emulsifying agent for the practice of this invention, but any fatty compound having at one end a fatty residue of 10 or more carbon atoms and no hydrophilic groups, and presenting at the other extremity an amine group, will be suitable. Examples of such compounds are fatty amines and the amides of the fatty acids with the'polyamines. As an acid residue'in such an amide there may be cited oleic acid, lauric acid, myristic acid, palmitic acid, stearlc acid, palmitoleic acid,'arachidic acid and the like. Instead ofthe pure acids the fatty acid residues contained in fats and oils, such as coconut oil, soyabean oil, lard, tallow, peanut oil, corn oil, hydrogenated soyabean oil, hydrogenated fish oil, and the like may be employed. The amide residue may be derived from an? polyamine such as ethylene diamine, diet-hylene triamine, ethanol ethylene diamine, tetraethylene pentamine, 1,3 diamino isopropanol and the like. Specific amides coming within the above requirements are exemplified in the amide produced by reacting oleic acid and ethylene diamine; rice oil with diethylene triamine; soyabean oil with diethylene triamine, hydrogenated soyabean oil Examples of suitable amines are stearyl amine, oleyl amine, lauryl amine, dilauryl amine, and the like.
Acetic acid was cited as a suitable acid for adjusting the pH of the cationic surface active amino compound. However, any acid may be used for this purpose, preferably a weak acid, in order that the pH may be adjusted more accurately and that a buffering action may be secured. A suiiicient amount of the acid is employed to reduce the pH ofthe amino compound to 6 or below when the amino compound is in 2% aqueous solution.
Petroleum oil was cited as an oil suitable -for theoily phase of emulsions according to this invention. However, any mineral, vegetable or animal oil, fat or wax, the viscosity of which is not too great to interfere with the inversion of the phases, may be employed. Mineral oils may vary in viscosity from about 35 seconds to 300 seconds Saybolt (100 F.) Suitable oils, other than mineral oils, are exemplified in soyabean oil, cottonseed oil, rice oil, peanut oil. corn oil, teaseed oil, neats-foot oil, cod oil, castor oil, whale.
immediately.
. to an oil-inwater emulsion as the'emulsion in taining mostly oil, which emulsion may be converted at the point of use into an oil-in-water.
emulsion without diiliculty or special equipment.
Further, the diluted and inverted emulsions have the propertiesunlike those'of most oil-in-water emulsions, in that they have a greasy feel and a tendency to prevent and destroy foam on any aqueous bodies containing them. Further, when these emulsions are added to any batch or stream of materials in" process, they will exert the same action as an unemulsified oil would, with the advantages that-a considerably less amount of actual oil is used, since the bulk of the emulsion will be constituted of water, and further, that the emulsion will subsequently disperse complete ly in the stock without separating and interfering at subsequent points in the process. For instance, the emulsions may be added to paper or glue stocks at.any point where foaming is encountered and will kill the foam at that point. However, the oil will eventually becom distributed thoroughly throughout the body of the stock and will not cause troubles such as, in the case of the paper, streaks in the paper web made therefrom, or in the case of glue, fish eyes on the coatings made therefrom. Further, these emulsions will not readily attack the rubber or other oil-sensitive materials contacted by the stock to which they are added.
For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely to further illustrate the invention, and are not'to be construed in a limiting sense, all parts given being by weight.
Example I 270 parts of #2 fuel oil, parts of the monoamide produced by reacting oleic acid with ethylene diamine, and 1 part of glacial acetic acid were mixed. 300 parts of water were added and mixed in with agitation to form. an emulsion of .water in oil. 200 additional parts of water were without breaking.
An emulsion of water in oil prepared as just described, but without having been diluted with water, was added to a stream of paper stock going to the vat of a cylinder machine, in which foaming was giving trouble.
" Example 11 270 parts of #2 fuel oil, 80 parts of the monoamide produced by the reaction of hydrogenated soyabean oil with ethanolethylene diamine, and 1 part of gracial acetic acid were mixed. 300 parts of water were added and mixed in with agitation to form an emulsion of water in oil. This emulsion exhibited the same capability of inversion The foam broke down Example I. The emulsion of this example had excellent defoaming properties.
Example III 30 parts of the monoamides formed by react.- ing a mixture of rice oil and cottonseed oil with diethylene triamine were substituted for the 'monoamides employed in the procedures of .Ex-
amples I and II. The resulting water-in-oil emulsions exhibited the same properties of ready inversion and of foam prevention as did the emulsions in Examples I and II.
Example IV The procedures of Examples I and II were repeated, using stearylamine in place of the mono sions which are readily inverted by mere dilu- 'tion and slight agitation. When such inversion occurs as the emulsions are added to aqueous,
stock, novel surface effects are obtained, similar to effects obtained by the use of unemulsifled oils. but without the difiiculties attending th use of unemulsifled oils. 4
Having described our invention, what we claim as new and desire to secure by. Letters Patent is:
'1. A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface acitve fatty amino compound, the fatty residue of which contains at least 10 carbonatoms and no hydrophilic groups, the amino compound being adjusted with acid to have a pH of about 6.0 cries in 2% aqueous solution.
2. A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting oleic acid and ethylene diamine, the monoamide being adjusted with acid to have a pH ofabout 6.0 or less in 2%. aqueous solution. v
3. A reversible emulsion of water in oil, the
active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting hydrog'e'nated soyabean oil with ethanol ethylene diamine, the monoamide being adjusted with acid to have a pH of about 6.0 or less in. 2% aqueous solution. I
4. A reversible emulsion of'water in oil, the active emulsifying ingredient of which comprises chiefly a fatty amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution. I
5.'A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly stearylamine, the stearylamine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
chiefly a cationic surface active fatty amino com-.
pound, the fatty residue of which contains at least carbon atoms and no hydrophilic groups,
the amino compound .being adjusted by means of acetic acid to have a pH of in 2% aqueous solution. l
7. A reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amidoamine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amido-amine being adjusted by means of acetic acid to have apH of about 6.0 or less in 2% aqueous solution.
8. A reversible emulsion of w ater in oil, the active emulsifying ingredient of which comprises about 6.0 or less chiefly the monoamide formed by reacting oleic,
acid and ethylene diamine, the monoamide being acfiusted by means of acetic acid to have 'a pH of about 6.0 or less in 2% aqueous solution.
9. A reversible emulsion of water in oil, the' active emulsifying ingredient of which comprises chiefly a fatty amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amine being adjusted by means of acetic acid to have a pH of about 6.0 or less in 2% aqueous solution.
10. A defoaming agent comprising oil, water and an emulsifying agent which compriseschiefly.
a cationic surface active fatty amide-amine, the
fatty residue of which contains at least. 10 carbon atoms and no hydrophilic groups, the amidoamine being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
11. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amino compound,
the fattyresidue of which contains at least 10 carbon atoms and no hydrophilic groups, the amino compound being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
12. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly a cationic surface active fatty amide-amine, the fatty residue of which contains at least 10 carbon atoms and no hydrophilic groups, the amido amine compound being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
13. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly the monoamide formed by reacting hydrogenated soyabean oil with ethanol ethylene diamine, the amide being adjusted with acid to have a pH of about 6.0 or less in 2% aqueous solution.
14. Method of suppressing foam in aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly 15. Method of suppressing foamin aqueous process fluids which comprises adding thereto a reversible emulsion of water in oil, the active emulsifying ingredient of which comprises chiefly stearylamine, the stearylamine being adjusted with acid to have a. pH of about 6.0 or less in 2% aqueous solution, I JAMES H. FRITZ.
EDWIN A. ROBINSOLL.
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US425856A US2347178A (en) | 1942-01-07 | 1942-01-07 | Reversible emulsion and application therefor |
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US425856A US2347178A (en) | 1942-01-07 | 1942-01-07 | Reversible emulsion and application therefor |
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Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2423214A (en) * | 1944-03-16 | 1947-07-01 | Paper Chemistry Inst | Foam prevention |
US2450534A (en) * | 1945-08-04 | 1948-10-05 | Huber Corp J M | Emulsion printing inks |
US2461730A (en) * | 1942-09-12 | 1949-02-15 | Dearborn Chemicals Co | Method of inhibiting foam formation in an aqueous gas-liquid system |
US2488515A (en) * | 1945-05-10 | 1949-11-15 | Nopco Chem Co | Utilization of waste wax paper |
US2493453A (en) * | 1944-10-28 | 1950-01-03 | Dearborn Chemicals Co | Prevention of foaming in steam generation |
US2563857A (en) * | 1945-10-12 | 1951-08-14 | Nopco Chem Co | Defoaming agent for pulp and paper stock |
US2563856A (en) * | 1945-10-12 | 1951-08-14 | Nopco Chem Co | Defoaming agent for pulp and paper stock |
US2600361A (en) * | 1948-06-09 | 1952-06-10 | Dearborn Chemicals Co | Prevention of foaming in steam generation |
US2639989A (en) * | 1946-04-25 | 1953-05-26 | United States Gypsum Co | Treatment of cellulosic pulps |
US2751358A (en) * | 1949-11-28 | 1956-06-19 | Shell Dev | Non-foaming detergents |
US2762780A (en) * | 1952-05-07 | 1956-09-11 | Hodag Chemical Corp | Antifoam compositions |
US2809168A (en) * | 1952-09-04 | 1957-10-08 | Swift & Co | Defoaming composition and process |
US2946746A (en) * | 1956-10-01 | 1960-07-26 | Union Oil Co | Oil-external emulsion drilling fluids |
US3169113A (en) * | 1961-07-17 | 1965-02-09 | Nalco Chemical Co | Emulsifier compositions and uses thereof |
US3437437A (en) * | 1966-10-05 | 1969-04-08 | Betz Laboratories | Control of foam formation in the synthesis of phosphoric acid |
DE2520028A1 (en) * | 1975-05-06 | 1976-11-11 | Stockhausen & Cie Chem Fab | LIQUID, STABLE POLYMER DISPERSIONS |
US6586479B2 (en) * | 2000-07-21 | 2003-07-01 | Clariant Gmbh | Process for preparing fine emulsions |
-
1942
- 1942-01-07 US US425856A patent/US2347178A/en not_active Expired - Lifetime
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2461730A (en) * | 1942-09-12 | 1949-02-15 | Dearborn Chemicals Co | Method of inhibiting foam formation in an aqueous gas-liquid system |
US2423214A (en) * | 1944-03-16 | 1947-07-01 | Paper Chemistry Inst | Foam prevention |
US2493453A (en) * | 1944-10-28 | 1950-01-03 | Dearborn Chemicals Co | Prevention of foaming in steam generation |
US2488515A (en) * | 1945-05-10 | 1949-11-15 | Nopco Chem Co | Utilization of waste wax paper |
US2450534A (en) * | 1945-08-04 | 1948-10-05 | Huber Corp J M | Emulsion printing inks |
US2563857A (en) * | 1945-10-12 | 1951-08-14 | Nopco Chem Co | Defoaming agent for pulp and paper stock |
US2563856A (en) * | 1945-10-12 | 1951-08-14 | Nopco Chem Co | Defoaming agent for pulp and paper stock |
US2639989A (en) * | 1946-04-25 | 1953-05-26 | United States Gypsum Co | Treatment of cellulosic pulps |
US2600361A (en) * | 1948-06-09 | 1952-06-10 | Dearborn Chemicals Co | Prevention of foaming in steam generation |
US2751358A (en) * | 1949-11-28 | 1956-06-19 | Shell Dev | Non-foaming detergents |
US2762780A (en) * | 1952-05-07 | 1956-09-11 | Hodag Chemical Corp | Antifoam compositions |
US2809168A (en) * | 1952-09-04 | 1957-10-08 | Swift & Co | Defoaming composition and process |
US2946746A (en) * | 1956-10-01 | 1960-07-26 | Union Oil Co | Oil-external emulsion drilling fluids |
US3169113A (en) * | 1961-07-17 | 1965-02-09 | Nalco Chemical Co | Emulsifier compositions and uses thereof |
US3437437A (en) * | 1966-10-05 | 1969-04-08 | Betz Laboratories | Control of foam formation in the synthesis of phosphoric acid |
DE2520028A1 (en) * | 1975-05-06 | 1976-11-11 | Stockhausen & Cie Chem Fab | LIQUID, STABLE POLYMER DISPERSIONS |
US6586479B2 (en) * | 2000-07-21 | 2003-07-01 | Clariant Gmbh | Process for preparing fine emulsions |
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