JPS6159777B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel liquid film formulations, i.e.
The above relates to an emulsion that is stable at temperatures below the boiling point of the internal phase of the emulsion and below about 120°C. The emulsion consists of an external phase that is immiscible with water and an internal phase that is surrounded by and immiscible with the external phase. ko〓〓〓〓
The external phase of is composed of an oil component and an additive, which acts both as a surfactant and as a membrane reinforcing agent. These additives are selected from polyamine derivatives and mixtures of these polyamine derivatives having the following general formula: (In the formula, n for the polyisobutylene part is
10 to 60, x is 3 to 10, and y is hydrogen, a nitrogen group containing hydrogen, a nitrogen group containing hydrogen and oxygen, an alkyl group having up to 10 carbon atoms, and nitrogen, oxygen, or both. and 10
(selected from the group consisting of alkyl groups having up to 1 carbon atoms). These emulsion formulations, especially at high temperatures,
It is useful wherever a stable water-in-oil emulsion is required. For example, the liquid film formulations of the present invention are useful for removing components dissolved in the aqueous treated phase, ie, the external phase, by trapping them in the internal phase of the emulsion. In this embodiment of entrapment, the external phase of the emulsion is permeable to the dissolved components, and the internal phase is a reactive agent capable of converting the dissolved components into a non-permeable form. Contains. In another embodiment, the liquid film formulation of the present invention can be used as a slow release mechanism. In this embodiment, the internal phase contains the components to be released from the emulsion. The component used in this slow release embodiment is only slightly soluble in the external phase of the emulsion, so it permeates through the external phase into the aqueous external phase over a period of time. When using the emulsion of the invention, there is no need to cool the phase to be treated before adding the emulsion. In contrast, cooling was often required when using prior art emulsion formulations. In the vast number of intended applications of liquid films,
The stability of liquid films is a very important property. This property is most important when emulsions are used to isolate the phase to be treated from the contents of the internal phase of the emulsion. This is because when the breakage of the emulsion occurs, this isolation property is lost. In liquid film technology, the importance of emulsion stability has been recognized and addressed by the development of a number of additives that can enhance emulsion stability. Such additives are of two different types: surfactants and reinforcing agents. Both reinforcing agents and surfactants increase emulsion stability, but these additives do not perform the same function. Surfactants are used at the interface between the "oil" and "aqueous" phases, i.e. between the aqueous treated phase and the oil phase of the emulsion and the interface between the oil phase and the aqueous internal phase of the emulsion. Both form essentially thin films, thereby improving the stability of the liquid film formulation. Reinforcing agents not only strengthen the interfaces between the various phases, but also the oil phase, ie the film itself. This effect can be achieved by increasing the viscosity of the membrane phase or by chemical interaction with the surfactant layer at the two interfaces mentioned above, either alone or in combination. The invention is not limited to any particular theory disclosed herein. Any theory described herein is presented for purposes of illustration only so that the invention may be better understood. In order to achieve two types of stability: stability of the oil film phase itself and stability of the interface, it was necessary to add a reinforcing component and a different surfactant component to the external phase of the emulsion. . However, such methods require emulsion manufacturing operations to be complicated because the emulsion formulator must carefully formulate several ingredients in specific amounts to create an emulsion that can be used in the desired process. It becomes complicated. Moreover, some surfactants and some reinforcing agents are completely incompatible, i.e., they interact to reduce the useful properties of each partner, or, under certain conditions, For example, they are incompatible under certain conditions of temperature, concentration, etc. All of the above formulation problems can be eliminated by using one additive that exhibits both surfactant and reinforcing functions. If you use one type of ingredient that performs two types of functions,
There are inherent advantages to this, but we have found that in addition to all these advantages there are also others. Water-in-oil emulsions obtained using any of the additives specified above under the ranges and conditions disclosed below are unexpectedly stable under high temperature conditions (e.g. above 100°C). It was found that the Emulsion formulations of the prior art are rarely stable above 85°C, whereas emulsion formulations of the present invention can be stable up to temperatures as high as 120°C. Biotechnology and Bioengineering
Bioengineering), Volume 17, pp. 1137-1156 (1975
Raam R. Mohan
R. Mohan) and Norman N. Li.
Nitrate and Nitrite Reduction by Complete Cell Encapsulated in Liquid Film
and Nitrite Reduction by Liquid Membrane
On page 1140 of “Encapsulated Whole Cells”,
ENJ-3029 is disclosed to be a polyamine that acts as both a reinforcing agent and a surfactant. However, this article does not disclose that the component of ENJ-3029 that has the above-mentioned effect belongs to the group of polyamine derivatives having the following general formula: (wherein n is 10 to 60, x is 3 to 10, and y is essentially a combination of two groups, one of which is an oxygen-containing hydrocarbon having up to 10 carbon atoms) group and the other is a nitrogen-containing hydrocarbon group having up to 10 carbon atoms). The above paper, without specifying the composition of ENJ-3029, incidentally merely discloses its dual capabilities and uses ENJ-3029 as a single surfactant and reinforcing component. No working examples are shown. The paper specifically describes the dual capabilities of ENJ-3029 on page 1140, which lists the specific oil phase components used in the disclosed work. This list includes 2% surfactant, Span-80, and 10% ENJ-
3029 is listed. Therefore, the authors of this paper
Although describing the possible dual capabilities of ENJ-3029, even the examples demonstrating this insight do not use it as a single surfactant-reinforcing agent. The authors of this paper used ENJ-3029 in combination with other surfactants. Furthermore, this article does not teach any lower or upper limits to the amount of ENJ-3029 that can be used to achieve such dual performance. Also, this article does not disclose any other conditional limitations or unexpected stability properties of these formulations, such as high temperature stability of emulsions using appropriate amounts of ENJ-3029. In fact, this paper does not disclose any emulsions used at temperatures above 33°C, much less teach emulsions using ENJ-3029 as a single surfactant and reinforcing agent at temperatures up to 120°C. I haven't. Water-in-oil emulsions whose external phase consists of an oil component and an additive selected from the group consisting of It has unexpectedly been discovered that polyamine derivatives and mixtures of these polyamine derivatives have the following general formula: (In the formula, n for the polyisobutylene part is
10 to 60, x is 3 to 10, and y is hydrogen, a nitrogen group containing hydrogen, a nitrogen group containing hydrogen and oxygen, an alkyl group having up to 10 carbon atoms, and nitrogen, oxygen or (selected from the group consisting of alkyl groups containing both and having up to 10 carbon atoms). The above-mentioned additives can be used individually in the oil external phase of the emulsion so as to perform both surfactant and reinforcing agent functions. The internal phase of the emulsion is an aqueous phase. This aqueous phase can be acidic or basic depending on its specific use.
It may also be neutral. The internal phase contains either one or more chemical agents for reacting with compounds diffusing from the treated phase or one or more chemical agents for diffusing into the treated phase. . In the present invention, the formulation of the liquid film (the external phase of the emulsion) is greatly simplified. In the present invention, an additive that functions as both a surfactant and a membrane reinforcing agent is dissolved in a solvent. This has the advantage of both simplifying the procedure for formulating membrane components and avoiding undesirable reactions between surfactants and reinforcing agents. A further advantage is that much higher temperature stability can be achieved than in the case of multi-component systems. Surfactants are usually small molecules that can become unstable at elevated temperatures for many reasons. Surfactants may chemically react with either the components in the treated phase in which the emulsion is dispersed or with the encapsulated phase. The instability of this surfactant is also due to its high solubility in the treated phase and/or the encapsulated phase.
Alternatively, it can also be caused by high surface activity, which means that the emulsion emulsifies the phase to be treated. Any of the above phenomena will result in an unstable liquid film composition even in the presence of a film reinforcing agent. In contrast, the present invention introduces a polar group onto the polymeric molecular chain so that the resulting molecule is both a surfactant due to its polar group and a membrane reinforcing agent due to its main chain of the polymeric molecule. Disclose what you will do. The compounds listed below greatly enhance the stability of the emulsion. This unexpected stability is due to the fact that all these compounds have polar groups attached to the polymeric molecular chain, and the polar groups confer surface activity on the compound and the polymeric backbone is attached to the compound. may arise from the fact that it imparts reinforcing properties to This combination results in unexpected stability properties. Although the situation is as described above, there are also other possible additives that can be used in the external phase as reinforcing agents and surfactants. Such additives include pour point depressants, sludge dispersants and viscosity index improvers used in lubricating oils. Again, the invention is not limited to any particular theory. The external phase of the emulsion consists of the oil component and additive components. Generally speaking, the oil component consists of a water-immiscible solvent selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers, higher oxygenated compounds such as alcohols, ketones, acids and esters. obtain. Of course, this oil component must be liquid under the conditions of use of the composition of the invention;
It must be capable of dissolving the specific additives selected above and, in cooperation with the specific additives, forming a stable water-in-oil emulsion with an internal phase. . In many applications, this internal phase is aqueous, but any solvent that will form and maintain a stable emulsion internal phase with the selected additive-oil component external phase mixture can be used. Careful selection of oil components is essential when using high temperatures and strong acids or bases. Solvents such as esters should not be used as they will be hydrolyzed to volume. Solvent volatility is another limitation. Therefore, hydrocarbons and other solvents that volatilize at 85°C or can be steam distilled should not be used. When using the compositions of the invention in water purification processes, solvents that leave toxic residues in the water must be avoided. Furthermore, in processes where it is necessary to easily separate the emulsion from the stream to be treated, such as water purification processes,
The oil component should be selected such that the specific gravity of the formulated emulsion differs from the specific gravity of the stream to be treated by at least about 0.025. The difference in specific gravity is approximately 0.025
If it is less than this, it will take time to separate the emulsion from the phase to be treated, which is not desirable. Other considerations will be apparent to those skilled in the art. For the reasons mentioned above, preferred solvents are selected from the following group: Petroleum fractions with a boiling point above 200°C. High boiling normal paraffins having melting points of 70° C. or higher should not be used unless these paraffins are mixed with other solvents to lower their melting points. Mildly due to halogens such as chlorine or benzene rings,
That is, paraffinic solvents substituted in an amount of less than 5 mol % can be used. Aromatic type solvents can also be used. A more preferable solvent is 6 to
100 carbon atoms, most preferably 10-65 carbon
It is a petroleum fraction such as isoparaffin having elementary atoms. An example of this type of solvent is purified isoparaffin, known as Solvent Neutral Type, available from Exxon Chemical Company. Almost all of these solvents are suitable for such applications, including, for example, Solvent Neutral 100, Solvent Neutral 150, Solvent Neutral 600, and various grades in between. indicates the viscosity (centistokes) at 37.8℃ (100〓). Other suitable solvents include the Isopar M series, also manufactured by Exxon Chemical. bright stock, Coray, petroleum lubricants with viscosities of 479.4 centistokes and 412.2 centistokes, respectively, at 37.8°C (100〓)
Other petroleum fractions such as 90 are also suitable. In many applications, e.g. solvent neutral
It is also desirable to use mixed solvents such as a combination of Solvent Neutral 100 and Solvent Neutral 600 or a combination of Solvent Neutral 100 and Isopar M. The additive is selected from the group consisting of: polyamine derivatives and mixtures of said polyamine derivatives having the following general formula: (In the formula, n for the polyisobutylene part is
10 to 60, x is 3 to 10, and y is hydrogen, a nitrogen group containing hydrogen, a nitrogen group containing hydrogen and oxygen, an alkyl group having up to 10 carbon atoms, and nitrogen, oxygen or (selected from the group consisting of alkyl groups containing both and having up to 10 carbon atoms). It has been unexpectedly discovered that the additives described above can function as surfactants and reinforcing agents in emulsions when added to the oil external phase. Emulsion formulations using the above-mentioned additives exhibit enhanced stability, especially at elevated temperatures, for example up to 120°C. Remaining stable means that these emulsion compositions remain substantially intact and membrane disruption is minimal. The stability of emulsions containing the above-mentioned additives in the external phase may be adversely affected at higher temperatures by the presence of components in the treated or encapsulated phase that chemically attack the above-mentioned additives at elevated temperatures. It should also be noted that Therefore, the additives according to the invention should not be used when there are components either in the treated phase or in the encapsulated phase that chemically react with these additives at elevated temperatures. For example, _H2S in wastewater
reacts strongly with the compound of formula () (ENJ-3029) at 80°C, resulting in the destruction of the emulsion. The additives described above are compatible with most other surfactants, reinforcing agents and liquid ion exchange agents of the prior art. Thus, emulsion formulations using the above-mentioned additives exhibit improved stability properties, but may optionally contain other compatible surfactants,
Stiffeners or liquid ion exchange agents can be added to this emulsion. The additive components represent from about 0.001% to about 50%, preferably from about 0.01% to about 30%, and most preferably from about 0.1% to about 10% by weight of the external phase. The internal phase can be any solvent that forms and maintains a stable emulsion internal phase with an external phase mixture of selected additive-oil components, as described above. This internal phase is immiscible with the external phase. Most conveniently the internal phase is an aqueous phase. The component or combination of components of the internal phase is selected primarily according to its intended use. The emulsions of this invention are useful whenever stable water-in-oil emulsions are required, especially at high temperatures. For example, the liquid film formulations of the present invention are useful for removing components dissolved in the aqueous treated phase, ie, the outer phase, by trapping the components in the inner phase of the emulsion. In this entrapment embodiment, the external phase of the emulsion is permeable to the dissolved components, and the internal phase contains a chemical agent capable of converting the dissolved components into an impermeable form. are doing. U.S. Pat. No. 3,779,907 discloses a method for removing dissolved components from an aqueous solution using certain water-in-oil emulsion formulations.
Ru. Similarly, this internal phase contains chemical agents that can convert dissolved components (those that permeate through the emulsion) into an impermeable form. The emulsion of the present invention can be used in place of the emulsion formulation disclosed in US Pat. No. 3,779,907 to provide the same removal of dissolved components. This patent specification describes the types of dissolved components that can be removed by the emulsion of the invention, chemical agents for the internal phase that are suitable for removing specific components, i.e. the selection and concentration of the chemical agent that converts it into a permeable form;
and solubilizing additives, if deemed necessary.
For example, the selection of liquid ion exchange agents is disclosed. In another embodiment, the liquid film formulations of the present invention can also be used as a slow release mechanism. In this embodiment, the internal phase of the emulsion contains the components to be released from the emulsion. The ingredients utilized in this slow release embodiment are only slightly soluble in the external phase of the emulsion;
This allows the component to permeate through the external phase of the emulsion into the aqueous external phase over an extended period of time. The rate of release depends on the extent to which the components of the internal phase to be released are dissolved in the external phase of the emulsion. The more soluble this component is in the external phase, the faster it will permeate out of the emulsion. One skilled in the art will be able to select the components of the external phase required for a certain release for a given chemical component present in the internal phase. This selection is based on the solubility of the given component in the particular external phase. This slow release embodiment can be used in a wide variety of applications. Ingredients that can be used in this slow release embodiment include pesticides, caustic or acidic ingredients for pH adjustment, pharmaceutical ingredients, fertilizers, or chemical agents to initiate some type of chemical reaction. The internal phase of the present invention is approximately 25% by weight of the total emulsion.
up to about 90% by weight, preferably about 33% to about 80% by weight. The emulsions of the present invention can be used under any pressure that allows the fluidity of the various phases to be maintained.
For convenience, atmospheric pressure is used in the examples. These emulsions also have a temperature of about -20 to about 120
C., preferably from about 0.degree. C. to about 100.degree. C., and most preferably from about 25.degree. C. to about 85.degree. The only restriction on the upper temperature limit is that it must be below the boiling point of any component of the emulsion. This occurs, for example, when the internal phase of the emulsion is aqueous and does not contain a sufficient amount of solute to raise the temperature of the internal phase to a predetermined level, for example 120°C. The following examples and reference examples are for illustrative purposes only and are not intended to limit the invention. Reference Examples 1-2 and Examples 1-2 The treated phase in Reference Examples 1-2 and Example 1 was a simulated wastewater phase containing 1000 ppm of phenol dissolved in water. The film phase is 2% span 80 in reference example 1 and 2% span -80 in reference example 2.
and 2% ENJ-3029, a compound of formula (), and in Example 1 3% ENJ-3029. Encapsulated chemical agent phase is 0.5% NaOH
It was an aqueous solution. The procedure for making the emulsion was the same for all three experiments. Add surfactant or membrane reinforcing agent or both to S100N
dissolved in it. The caustic solution to be encapsulated was then poured into the oil phase with stirring to form an emulsion. The weight ratio of caustic solution:oil phase was 1:2. This emulsion was gently mixed with the liquid to be treated at a weight ratio of 1:1. Stirring was stopped from time to time to sample the treated phase. Reference example 1
-2 and Example 1 were carried out at 25°C. A sample of the treated phase was analyzed to determine the concentration of phenol.
The results were as shown in Table 1. Comparing the phenol removal results obtained in Reference Examples 1 and 2 and Example 1, it is clear that even when a surfactant such as Span 80 is used alone, it is stable and effective for removing phenol from an aqueous solution of phenol. It turns out that it is not possible to create an effective liquid film emulsion.
Stable emulsions were obtained when Span-80 was used in combination with a membrane reinforcement such as ENJ-3029. An emulsion with a stability substantially equal to that of Reference Example 2 was used as a surfactant and membrane reinforcing agent by ENJ.
- Obtained by using only 3029. in this way,
Example 1 demonstrates that it is not necessary to use both separate surfactant and reinforcement components to create a stable emulsion. This is both an opportunity〓〓〓〓
This was achieved using an additive (in this case, ENJ-3029) that exhibits this ability. The effective removal rates shown in Reference Example 2 and Example 1 compared to the removal rates of Reference Example 1 were attributed to the higher stability of the emulsion formulations of Reference Example 2 and Example 1. This high stability minimized breakage of the emulsion of Reference Example 1. The emulsion formulations of Reference Example 2 and Example 1 minimized emulsion breakage, resulting in more effective phenol removal rates according to Reference Example 2 and Example 1. The membrane phase and treated phase in Example 2 were the same as in Example 1. The encapsulated internal phase is 30
% NaOH solution. The weight ratio of caustic solution to oil phase and the weight ratio of emulsion to treated phase were the same as used in each of the Reference Examples and Examples above. The temperature in this experiment was also 25°C. The results were as shown in Table 1. A high removal rate of phenols could be achieved due to the low destruction of the emulsion formulation using ENJ-3029. This formulation is
An even higher concentration of caustic solution (0.5% in Reference Example 1)
In contrast, Example 2 remained stable despite using 30% NaOH). It should be noted that ENJ-3029 is a mixture of compounds with the following structure suspended in a mineral with a viscosity of 20 centipoise: where m is an integer of about 40, so the molecular weight of this polyamine derivative is about 2000.

[Table] Reference Example 3 and Example 3 The membrane phase and encapsulated phase in these Reference Examples and Examples are the same as those used in each of the Reference Examples and Examples above, that is, Reference Example 3.
The membrane phase in Example 3 was the same as that used in Example 1, while the membrane phase in Example 3 was the same as that used in Example 1. The procedure for making the emulsion was the same as that used in each of the previous examples. After making the emulsions, put these emulsions into a stainless steel cylinder and boil them in one hour.
Heated to 110°C. The emulsion was then cooled to room temperature and observed. In Reference Example 3, about 1/3 of the emulsion was separated into oil and caustic layers. However, the emulsion made in Example 3 showed no phase separation and remained stable. in this way,
ENJ acts alone as a surfactant and reinforcing agent.
The formulation of Example 3 using 3029 remained stable at elevated temperatures. Example 4 The phase to be treated in Example 4 was a sulfuric acid solution (PH=
2.5) was a simulated mine leach solution containing 448 ppm copper dissolved as copper sulfate. The membrane phase is 1
% ECA4360 (which is sold by Exxon Chemical Company and whose structure is ENJ except that y is a hydrogen-containing nitrogen group)
- similar in structure to 3029), 5% LiX64N (which is an oxime-type copper complexing agent manufactured by General Mills), 11% S100N, and 83% Isopar M (which is an isoparaffin solvent). ). The encapsulated chemical phase was _an aqueous _solution of 14% _H2SO4 and 13% _CuSO4.5H2O . CuSO ₄ was included in the chemical phase to simulate the working agent emulsion. The procedure for making the emulsion was the same as in each of the previous examples. Encapsulation phase: oil phase weight ratio is 1:1
〓〓〓〓
It was hot. This emulsion was gently mixed with the phase to be treated in a weight ratio of 1:9. Mixing was stopped from time to time to sample the treated phase. The treated sample was analyzed to determine the copper concentration. the result,
It showed very good separation of copper. That is, in 12 minutes, the copper concentration in the treated phase decreased to a value exceeding the detection limit of standard colorimetric analysis of copper concentration.

[Table] Example 5 and Reference Examples 4 to 7 The 20% by weight aqueous sulfuric acid solution was added to the oil in a suitable container under stirring conditions so as to emulsify the sulfuric acid solution in the oil containing the surfactant and membrane reinforcing agent. The sulfuric acid solution was emulsified in various combinations of oil, surfactant, and membrane reinforcement by adding . The weight ratio of surfactant-containing oil to sulfuric acid solution is in all cases
The ratio was 1.5 to 1. In each case, the emulsion produced as described above was added to the aqueous feed phase (which was essentially an aqueous ammonium hydroxide solution with an ammonia concentration of 4048 ppm) under stirring conditions, and the ammonia solution was added to the ammonia solution. produced emulsion globules. The emulsion globules consisted of a surfactant-containing oily phase as a dispersed phase containing micro droplets of an aqueous sulfuric acid solution therein. Gentle stirring was continued to keep the emulsion globules suspended in the ammonium hydroxide solution. The concentration of ammonia in the ammonium hydroxide solution was then determined as a function of time using the well-known Kjeldahl method (Kjeldahl micromeasurement of nitrogen) according to ASTM E-147-61.
In the following, the ammonium hydroxide solution will be referred to as a feed solution. In all cases the weight ratio of feed solution to emulsion was 6.5:1. The same mixer was used for each example and reference, and the mixer speed was kept constant at 500 rpm for each example and reference to maintain emulsion globules suspended in the feed solution. The composition (wt%) of the surfactant-containing oil phase for each Example and Reference Example was as follows: Reference Example 4: 1% Span 80, 20% H300 and
LOPS of 79%. Reference example 5: 1% span 80 and 99% LOPS. Example 5: 1% ECA-4360 and 99%
LOPS. Reference example 6: 0.5% ECA-4360, 0.5% span 80
and 99% LOPS. Reference example 7: 0.6% ECA-4360, 0.6% span 80
and 98.8% LOPS. In addition, Span 80 and ECA-4360 are as described above, H300 is an oil-soluble polyisobutylene material used as a membrane reinforcing agent, and LOPS contains 3% aromatic substances and has a temperature of 1.71 at 100〓 (37.8℃). It is a light oil paraffinic solvent with a viscosity of centipoise, a flash point of 152〓 (66.7℃) and a specific gravity of 0.795 at 70〓 (21.1℃). The above results are shown in Table 3.

[Table] After mixing
Ammonia is extracted from the feed phase into the internal aqueous phase of the emulsion, which is an aqueous sulfuric acid solution, and the ammonia concentration in this feed phase is reduced.
However, if the membrane, ie, the surfactant-containing oil phase, is weak, upon continuous mixing action, the extracted ammonia is released back into the feed phase due to membrane breakdown. This is indicated by the increase in ammonia concentration in the feed phase as a function of elapsed time. In all Reference Examples 4-7 above, the ammonia concentration in the feed solution decreases after the first 10 minutes of mixing, but increases progressively with each subsequent 10 minutes of mixing. That is, extraction of ammonia occurs initially, but after a mixing time of approximately 10 minutes, the membrane, i.e., the surfactant-containing oil phase, weakens and begins to break down, thus releasing the previously extracted ammonia. and returned to the feed solution. Contains only 1% by weight of ECA-4360〓〓〓〓
In Example 5 of the present invention, the above phenomenon does not occur, and ammonia continues to be extracted from the feed solution. Therefore, ECA-4360 is a more effective single surfactant and membrane reinforcement agent than any of the other combinations listed above, even at lower concentrations than the combination of ECA-4360 and Span 80. is clear. 〓〓〓〓

Claims (1)

[Claims] 1. Consisting of an external phase and an internal phase surrounded by the external phase, the external phase is immiscible with water and is commonly used as an oil component and a single surfactant and reinforcing agent. formula: (In the formula, n for the polyisobutylene part is
10 to 60, x is 3 to 10, and y is hydrogen, a nitrogen group containing hydrogen, a nitrogen group containing hydrogen and oxygen, an alkyl group having up to 10 carbon atoms, nitrogen, oxygen, or both. and 10
and an additive selected from the group consisting of a polyamine derivative having an alkyl group having up to Approximately 0.001% by weight of
~50% by weight, the internal phase is immiscible with the external phase, and the internal phase comprises from about 25% to about 90% by weight of the total emulsion. , about -20°C to about 120°C and below the boiling point of any component of the emulsion. 2. The emulsion of claim 1, wherein the emulsion is stable at about 0°C to about 100°C. 3. The emulsion of claim 2, wherein the additive comprises from 0.01% to about 30% by weight of the external phase. 4. The emulsion of claim 3, wherein the internal phase accounts for about 33% to 80% by weight of the total emulsion. 5. The emulsion of claim 2, wherein the emulsion is stable at about 25°C to about 85°C. 6. An emulsion according to claim 3, wherein the internal phase further contains a reactant capable of converting the permeable component into a non-permeable form.