Composite emulsifier composition, composite emulsifier and method of manufacturing the same

Abstract

The present invention provides a composite emulsifier composition, a composite emulsifier and method of manufacturing the same. The composite emulsifier composition includes a specific ratio of cis-oleic acid and saturated fatty acids. The addition of saturated fatty acids can beneficially lower the surface tension of cis-oleic acid, thereby allowing the composite emulsifier to be effectively applied in emulsion polymerization reactions.

Description

[Technical Field]

[0001] This invention relates to a composite emulsifier composition, a composite emulsifier and a method for manufacturing the same, and particularly to a composite emulsifier composition comprising cis oleic acid and saturated fatty acids, a composite emulsifier and a method for manufacturing the same. [Previous Technology]

[0002] In emulsion polymerization, emulsifiers reduce the surface tension between the monomers and the aqueous phase by coating the hydrophobic monomers, allowing them to disperse uniformly in the aqueous phase and form stable microdroplets. This effectively prevents monomer aggregation and sedimentation, thus promoting free radical polymerization. Furthermore, emulsifiers can control the growth and distribution of polymer particles, thereby affecting the final polymer's particle size, morphology, and physical properties, making them an indispensable auxiliary in emulsion polymerization.

[0003] The main component of emulsifiers used in general emulsion polymerization is trans-oleic acid (hereinafter referred to as trans-oleic acid). It has low surface tension, high stability, and is not easily rancid, providing strong protection for monomer droplets and ensuring the smooth progress of the emulsion polymerization reaction. However, since trans-oleic acid does not exist in nature, there may be risks such as supply shortages and price increases. In contrast, cis-oleic acid can be extracted from plants and animals in nature, making it easier to obtain and having more suppliers. However, due to its higher surface tension, difficulty in storage, and greater steric hindrance, cis-oleic acid provides relatively weaker protection for monomer droplets and cannot directly replace trans-oleic acid in conventional emulsifiers.

[0004] In view of this, there is an urgent need to provide a composite emulsifier composition, a composite emulsifier and a method for manufacturing the same, in order to solve the above problems. [Summary of the Invention]

[0005] In view of the above problems, one aspect of the present invention is to provide a composite emulsifier composition comprising cis isomers of oleic acid and saturated fatty acids for use in emulsification polymerization reactions.

[0006] Another aspect of the present invention is to provide a method for manufacturing a composite emulsifier, which involves obtaining the composite emulsifier by melting and saponification steps of the above-mentioned composite emulsifier composition.

[0007] Another aspect of the present invention is to provide a composite emulsifier, which is prepared by the above-described method.

[0008] According to one aspect of the present invention, a composite emulsifier composition is provided, comprising fatty acids, wherein the fatty acids include oleic acid and saturated fatty acids, the oleic acid being a cis isomer, and based on the fatty acids being 100 wt%, the oleic acid being 80 wt% to 90 wt%, and the saturated fatty acids being 10 wt% to 20 wt%; and a potassium hydroxide solution.

[0009] According to one embodiment of the present invention, the aforementioned saturated fatty acid has 16 to 18 carbon atoms.

[0010] According to another aspect of the present invention, a method for manufacturing a composite emulsifier is provided, the method comprising: mixing fatty acids and water to obtain an emulsifying solvent, wherein the fatty acids include oleic acid and saturated fatty acids, the oleic acid being a cis isomer, and based on 100 wt% of fatty acids, 80 wt% to 90 wt% of oleic acid and 10 wt% to 20 wt% of saturated fatty acids; performing a melting step on the emulsifying solvent to obtain a molten emulsifying solvent; and performing a saponification step on the molten emulsifying solvent to obtain a composite emulsifier, wherein the saponification step comprises adding a potassium hydroxide solution to the molten emulsifying solvent.

[0011] According to one embodiment of the present invention, the aforementioned saturated fatty acid has 16 to 18 carbon atoms.

[0012] According to one embodiment of the present invention, the melting temperature of the aforementioned melting step is 65°C to 75°C.

[0013] According to one embodiment of the present invention, the melting time of the aforementioned melting step is 1 hour to 2 hours.

[0014] According to one embodiment of the present invention, the saponification temperature of the aforementioned saponification step is 65°C to 75°C.

[0015] According to one embodiment of the present invention, the saponification time of the aforementioned saponification step is 2 to 4 hours.

[0016] According to another aspect of the present invention, a composite emulsifier is provided, which is prepared by the above-described method for manufacturing composite emulsifiers.

[0017] According to one embodiment of the present invention, the concentration of the aforementioned composite emulsifier is 5 wt% to 30 wt%.

[0018] The composite emulsifier composition and manufacturing method of the present invention utilize readily available and inexpensive cis-oleic acid to replace trans-oleic acid in conventional emulsifier compositions, which can significantly reduce raw material costs and avoid the risk of raw material shortages. Furthermore, by adding saturated fatty acids, the surface tension of cis-oleic acid can be effectively reduced, enabling the resulting composite emulsifier to be effectively applied in emulsion polymerization reactions.

Implementation Method

[0019] The manufacture and use of embodiments of the present invention will be discussed in detail below. However, it will be understood that the embodiments provide many applicable inventive concepts that can be implemented in a wide variety of specific situations. The specific embodiments discussed are for illustrative purposes only and are not intended to limit the scope of the invention.

[0020] In this document, the range represented by "one value to another value" is a summary representation that avoids listing all the values ​​in the range in the specification. Therefore, the description of a particular value range covers any value within that value range as well as the smaller value range defined by any value within that value range, just as if the arbitrary value and the smaller value range were explicitly stated in the specification.

[0021] As described above, the composite emulsifier composition and manufacturing method of the present invention utilize readily available and inexpensive cis-oleic acid to replace trans-oleic acid in conventional emulsifier compositions, which can significantly reduce raw material costs and avoid the risk of raw material shortages. Furthermore, by adding saturated fatty acids, the surface tension of cis-oleic acid can be effectively reduced, enabling the resulting composite emulsifier to be effectively applied in emulsion polymerization reactions.

[0022] The composite emulsifier composition of the present invention includes fatty acids and potassium hydroxide solution. In one embodiment, the fatty acids include oleic acid and saturated fatty acids, and the oleic acid is a cis isomer. It should be noted that "oleic acid" here refers to cis-oleic acid with 18 carbon atoms and a single double bond. Replacing trans-oleic acid in conventional emulsifier compositions with cis-oleic acid can significantly reduce raw material costs and avoid the risk of raw material shortages. However, due to the large steric hindrance and surface tension of cis-oleic acid, its coating effect on monomer droplets is poor in emulsion polymerization reactions, and it is not easy to form microcells, making it difficult to obtain a suitable emulsion powder size in the subsequent acid precipitation stage of the emulsion. Therefore, it cannot directly replace trans-oleic acid in conventional emulsifiers as a component of the emulsifier. Therefore, the present invention improves the emulsification effect of the composite emulsifier in emulsion polymerization reactions by adding saturated fatty acids with lower surface tension to cis-oleic acid to reduce the steric hindrance and surface tension of cis-oleic acid.

[0023] In some embodiments, the carbon number of the saturated fatty acid may be, for example, 16 to 18, preferably 18. By adding a saturated fatty acid with 18 carbons—stearic acid—to cis oleic acid, it is better compatible with cis oleic acid with 18 carbons and its reactivity is increased.

[0024] In some embodiments, the fatty acid content is 100 wt%, oleic acid is about 80 wt% to about 90 wt%, and saturated fatty acid is about 10 wt% to about 20 wt%. If the amount of saturated fatty acid added is less than 10 wt%, the surface tension of cis-oleic acid cannot be effectively reduced, resulting in poor emulsification effect of the composite emulsifier. Conversely, if the amount of saturated fatty acid added is greater than 20 wt%, the overall fatty acid content is too viscous or precipitates may appear, making it impossible to mix evenly, which is detrimental to subsequent process operations.

[0025] In some specific examples, the amount of potassium hydroxide added is calculated based on the saponification value of the fatty acid, for example: fatty acid saponification value x (mg KOH / g), meaning that 1g of fatty acid requires x (mg) KOH for saponification. In this embodiment, the saponification value of the fatty acid is approximately 185 (mg KOH / g) to approximately 195 (mg KOH / g). Generally, the actual amount of potassium hydroxide added will be 5% to 10% more than the estimated amount to ensure the integrity of subsequent saponification steps.

[0026] Please refer to Figure 1, which is a flowchart illustrating a method 100 for manufacturing a composite emulsifier according to some embodiments of the present invention. First, operation step 101 is performed, in which fatty acids and water are mixed to obtain an emulsifying solvent. In some embodiments, the fatty acids comprise the aforementioned cis-oleic acid and saturated fatty acids, wherein based on 100 wt% of fatty acids, oleic acid comprises about 80 wt% to about 90 wt%, and saturated fatty acids comprise about 10 wt% to about 20 wt%. In some embodiments, the number of carbon atoms in the saturated fatty acids may be, for example, 16 to 18, preferably 18.

[0027] Next, step 103 is performed to melt the emulsified solvent to obtain a molten emulsified solvent. In some embodiments, the melting temperature of the melting step may be about 65°C to about 75°C, and the melting time may be about 1 hour to about 2 hours. The above-mentioned melting temperature and melting time facilitate the complete melting of saturated fatty acids, which are solid at room temperature, into a liquid and uniform mixing with cis-oleic acid.

[0028] In some embodiments, the melting step may include a stirring step to accelerate the melting of saturated fatty acids and to ensure uniform mixing of saturated fatty acids and cis-oleic acid. In some embodiments, the stirring speed of the stirring step may be, for example, 58 rpm, but the invention is not limited thereto.

[0029] Subsequently, step 105 is performed to saponify the molten emulsion solvent to obtain a composite emulsifier. In this embodiment, the saponification step includes adding a potassium hydroxide solution to the molten emulsion solvent to facilitate the saponification reaction. In some embodiments, the saponification temperature of the saponification step can be from about 65°C to about 75°C, and the saponification time can be from about 2 hours to about 4 hours. By using this specific range of saponification temperature and saponification time, complete saponification of the molten emulsion solvent can be ensured, so that the obtained composite emulsifier has better stability.

[0030] In some embodiments, the saponification step may include a stirring step to facilitate uniform mixing of the molten emulsion solvent and the potassium hydroxide solution and to ensure complete saponification. In some embodiments, the stirring speed of the stirring step may be, for example, 58 rpm, but the invention is not limited thereto.

[0031] In some embodiments, the concentration of the composite emulsifier is from about 5 wt% to about 30 wt%. The composite emulsifier in this concentration range can effectively exert its emulsification and polymerization capabilities in subsequent application processes, while avoiding excessive viscosity due to excessive concentration, which would affect the stirring operation.

[0032] As described above, the composite emulsifier composition and manufacturing method of the present invention utilize readily available and inexpensive cis-oleic acid to replace trans-oleic acid in conventional emulsifier compositions, which can significantly reduce raw material costs and avoid the risk of raw material shortages. Furthermore, by adding saturated fatty acids, the surface tension of cis-oleic acid can be effectively reduced, enabling the resulting composite emulsifier to be effectively applied in emulsion polymerization reactions.

[0033] The following examples illustrate the application of the present invention, but they are not intended to limit the invention. Those skilled in the art can make various modifications and refinements without departing from the spirit and scope of the invention. Example 1

[0034] The fatty acid composition of the composite emulsifier in Example 1 contains 90 wt% cis oleic acid and 10 wt% stearic acid. The composite emulsifier composition of Example 1 was used to prepare a composite emulsifier using the above-described method for manufacturing composite emulsifiers, and the surface tension values ​​of the composite emulsifier at different concentrations were measured using a surface tension meter.

[0035] In addition, the composite emulsifier of Example 1 was applied to the production process of rubber acrylic polymer, and the wet powder diameter of the emulsion obtained after adding hydrochloric acid solution to the emulsion was measured during the acid precipitation stage. Examples 2 and 3 and Comparative Examples 1 to 3

[0036] Examples 2 and 3, and Comparative Examples 1 to 3, were prepared using the same manufacturing method as Example 1, except for the proportion of fatty acids. The proportion of fatty acids in Examples 2 and 3 and Comparative Examples 1 to 3 can be found in Table 1 below, and the surface tension values ​​of the prepared composite emulsifiers at different concentrations were measured respectively.

[0037] The composite emulsifiers of Example 3, Comparative Example 1, and Comparative Example 3 were respectively applied in the production process of rubber acrylic polymers, and emulsified with butadiene, styrene, methyl methacrylate, cumene peroxide, and sodium formaldehyde sulfoxylate to generate emulsions. The pressure change in the reaction overlap section of the emulsification polymerization reaction was measured.

[0038] In addition, during the acid precipitation stage of the production process of rubber acrylic polymer using the composite emulsifiers of Example 3 and Comparative Example 1, the wet powder diameter of the emulsion obtained after adding hydrochloric acid solution to the emulsion was measured. Surface tension was also measured.

[0039] After cleaning the platinum plate, fix it on a surface tension meter (KRÜSS-K100). Then, pour a specific concentration of composite emulsifier into a glass beaker and place it on the stage of the surface tension meter. Next, raise the glass beaker until the liquid level of the composite emulsifier is close to the lower edge of the platinum plate (approximately 1 to 2 mm). Then, start the instrument to measure the surface tension value of the composite emulsifier. The measurement results are shown in Table 1 below. Particle size characterization analysis

[0040] Pour the emulsion into a particle size analyzer (BECKMAN COULTER-LS 13 320) and start the instrument to analyze the particle size of the emulsion. The resulting particle size characterization analysis chart is shown in Figure 2B.

[0041] Table 1

[0042] As shown in Table 1, compared with the composite emulsifier of Comparative Example 1, the composite emulsifiers of Examples 1 to 3 have lower surface tension values ​​at different concentrations, and are closer to the surface tension value of Comparative Example 3 (a conventional emulsifier). This indicates that adding an appropriate proportion of stearic acid to cis-oleic acid can effectively reduce the surface tension of the composite emulsifier and achieve a surface tension value similar to that of the conventional emulsifier. In addition, Comparative Example 2, due to its high proportion of stearic acid in the fatty acids (greater than 20 wt%), is prone to precipitation during the manufacturing process, resulting in uneven emulsifier production.

[0043] As can be seen from the reaction curve 201 of the reaction overlap section shown in Figure 2A, compared with the composite emulsifier of Comparative Example 1, the pressure drop rate of the composite emulsifier of Example 3 in the reaction overlap section is closer to that of Comparative Example 3 (conventional emulsifier). This is because the composite emulsifier of Example 3 has a lower surface tension value and a better emulsification effect.

[0044] Generally, if the emulsifier reacts normally in the preceding emulsification polymerization process, the resulting emulsion can be adjusted by changing the acid precipitation conditions to obtain a suitable powder size and distribution (e.g., 400 μm to 700 μm) to avoid the false specific gravity of the final product after dehydration and drying due to excessively coarse powder that cannot be improved by adjusting the acid precipitation conditions. As shown in Figure 2B, the particle size characterization analysis diagram 203 shows that, compared with Comparative Example 1, the emulsions obtained by the composite emulsifiers of Examples 1 and 3 in the production process have a more suitable wet powder size.

[0045] According to the above embodiments, the surface tension and emulsification effect of the composite emulsifier directly or indirectly affect the reaction process and finished product characteristics of the polymer. Therefore, the composite emulsifier composition and manufacturing method of the present invention utilize readily available and inexpensive cis-oleic acid to replace trans-oleic acid in conventional emulsifier compositions, which can significantly reduce raw material costs and avoid the risk of raw material shortages. In addition, by adding saturated fatty acids, the surface tension of cis-oleic acid can be effectively reduced, so that the obtained composite emulsifier can be effectively applied in emulsion polymerization reactions.

[0046] Although the present invention has been disclosed above by way of embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field to which the present invention pertains may make various modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims. [Simplified Explanation of the Diagram]

[0047] To gain a more complete understanding of the embodiments and advantages of the present invention, please refer to the following description and corresponding figures. It must be emphasized that the various features are not depicted to scale and are for illustrative purposes only. The relevant figures are explained below: Figure 1 is a flowchart illustrating a method for manufacturing a composite emulsifier according to some embodiments of the present invention. Figure 2A is a reaction curve showing the reaction overlap stage of the composite emulsifier in the rubber-acrylic polymer process according to some embodiments of the present invention. Figure 2B is a particle size characterization analysis diagram showing the composite emulsifier in the acid precipitation stage of the rubber-acrylic polymer process according to some embodiments of the present invention. [Biomaterial Storage]

[0049] Domestic storage information (please note in order of storage institution, date, and number): None. International storage information (please note in order of storage country, institution, date, and number): None.

Claims

1. A composite emulsifier composition, comprising: A fatty acid comprising oleic acid and a saturated fatty acid, the oleic acid being a cis isomer, the saturated fatty acid having 16 to 18 carbon atoms, and based on the fatty acid being 100 wt%, the oleic acid being 80 wt% to 90 wt%, and the saturated fatty acid being 10 wt% to 20 wt%; and a potassium hydroxide solution.

2. A method for manufacturing a composite emulsifier, comprising: A fatty acid and water are mixed to obtain an emulsifying solvent, wherein the fatty acid comprises oleic acid and a saturated fatty acid, the oleic acid being a cis isomer, the saturated fatty acid having 16 to 18 carbon atoms, and based on 100 wt% of the fatty acid, 80 wt% to 90 wt% of the oleic acid, and 10 wt% to 20 wt% of the saturated fatty acid; the emulsifying solvent is subjected to a melting step to obtain a molten emulsifying solvent; the molten emulsifying solvent is subjected to a saponification step to obtain a composite emulsifier, wherein the saponification step includes adding a potassium hydroxide solution to the molten emulsifying solvent.

3. The method for manufacturing the composite emulsifier as described in claim 2, wherein one of the melting steps has a melting temperature of 65°C to 75°C.

4. A method for manufacturing a composite emulsifier as described in claim 2, wherein the melting time of one of the melting steps is 1 hour to 2 hours.

5. A method for manufacturing a composite emulsifier as described in claim 2, wherein one of the saponification steps is performed at a saponification temperature of 65°C to 75°C.

6. A method for manufacturing a composite emulsifier as described in claim 2, wherein one of the saponification steps has a saponification time of 2 to 4 hours.

7. A composite emulsifier, which is prepared by a method for manufacturing a composite emulsifier as described in any one of claims 2 to 6.

8. The composite emulsifier as described in claim 7, wherein one of the composite emulsifiers has a concentration of 5 wt% to 30 wt%.

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