Preparation method of fatty acid phytosterol ester, fatty acid phytosterol ester and cosmetic

Abstract

The invention provides a preparation method of fatty acid phytosterol ester, the fatty acid phytosterol ester and cosmetics. The preparation method of the fatty acid phytosterol ester comprises the following steps: fatty acid and an alcohol compound are esterified in the presence of a catalytic effective amount of dodecylbenzene sulfonic acid to generate the fatty acid phytosterol ester, and the alcohol compound comprises phytosterol. The fatty acid phytosterol ester prepared by the method provided by the invention has the characteristics of low oxidation degree, low acid value and low moisture, and is beneficial to being used as a cosmetic raw material.

Description

Technical Field

[0001] The present application belongs to the field of cosmetics, and specifically relates to a preparation method of fatty acid phytosterol ester, fatty acid phytosterol ester and cosmetics. Background Art

[0002] Phytosterols are the basic chemical components of plants, including β-sitosterol, brassicasterol, stigmasterol, campesterol, etc. The structure of phytosterols contains a steroid nucleus with a hydroxyl group at the 3-position of the steroid nucleus. Under certain conditions, phytosterols can react with fatty acids and their esters to form fatty acid phytosterol esters.

[0003] Fatty acid phytosterol esters can replace lanolin as a cosmetic raw material. Fatty acid phytosterol esters can delay the penetration of water through the epidermis and increase the moisture content of the skin. Fatty acid phytosterol esters also have a high refractive index, which can bring gloss to cosmetics. In the related art, fatty acid phytosterol esters are prepared by plant sterols and fatty acids, and catalysts and solvents are introduced to accelerate the reaction rate. The introduced catalysts include sodium methoxide, dichlorothionyl, copper nitrate, etc. The introduced catalysts and solvents are corrosive and toxic, making the prepared fatty acid phytosterol esters unfavorable for use as a raw material for cosmetics. Summary of the invention

[0004] The present application provides a method for preparing fatty acid phytosterol esters, fatty acid phytosterol esters and cosmetics, aiming to ensure the preparation rate of fatty acid phytosterol esters and reduce or avoid the residue of toxic catalysts and solvents in fatty acid phytosterol esters.

[0005] The first aspect of the present application provides a method for preparing fatty acid phytosterol esters, the method comprising:

[0006] In the presence of a catalytically effective amount of dodecylbenzenesulfonic acid, fatty acids and alcohol compounds are esterified to generate fatty acid phytosterol esters, wherein the alcohol compounds include phytosterols.

[0007] In some embodiments, the method comprises:

[0008] Providing a mixture of fatty acids and alcohol compounds;

[0009] A catalytically effective amount of dodecylbenzene sulfonic acid is added to the mixture. The dodecylbenzene sulfonic acid is used as a catalyst to catalyze the esterification reaction of fatty acids and phytosterols to obtain fatty acid phytosterol esters. The esterification reaction temperature is 80°C to 120°C.

[0010] In some embodiments, dodecylbenzenesulfonic acid is used as a catalyst to catalyze the esterification reaction between fatty acids and phytosterols to obtain fatty acid phytosterol esters, including:

[0011] The fatty acid and the phytosterol undergo an esterification reaction at a first temperature T1 and a first pressure P1 to obtain fatty acid phytosterol esters;

[0012] distilling the fatty acid phytosterol ester at a second temperature T2 and a second pressure P2 to purify the fatty acid phytosterol ester;

[0013] Among them, T1, T2∈[80℃~120℃], P1>P2, P2<101.325kPa.

[0014] In some embodiments, the fatty acid and the phytosterol are esterified at a first temperature T1 and a first pressure P1 for a first time period, and the first time period is 2 hours to 6 hours.

[0015] In some embodiments, the fatty acid phytosterol esters are distilled at a second temperature T2 and a second pressure P2 for a second time period, wherein the second time period is 1 hour to 6 hours.

[0016] In some embodiments, after the fatty acid and the phytosterol are esterified at a first temperature T1 and a first pressure P1 to obtain the fatty acid phytosterol ester, the fatty acid phytosterol ester is distilled at a second temperature T2 and a second pressure P2, and before the fatty acid phytosterol ester is purified, the preparation method further comprises:

[0017] When the acid value of the fatty acid phytosterol ester is less than the first preset acid value, sodium bicarbonate is added to neutralize the acid value of the fatty acid phytosterol ester to a second preset acid value, and the first preset acid value is greater than the second preset acid value.

[0018] In some embodiments, the mass of dodecylbenzenesulfonic acid is 0.1-1% w / w of the total mass of the fatty acid and the alcohol compound.

[0019] In some embodiments, in the fatty acid and alcohol compounds, the ratio of the number of hydroxyl groups to the number of carboxyl groups is (0.5-1.5): (0.5-1.5).

[0020] In some embodiments, the phytosterol is one or a mixture of any proportion of sitosterol, stigmasterol, campesterol, and brassicasterol;

[0021] The fatty acid is a mixture of one or more of fatty acids having 8 to 36 carbon atoms, polymerized fatty acids, and aliphatic amino acids in any ratio.

[0022] A second aspect of the present application provides a fatty acid phytosterol ester, which is prepared by the preparation method of the fatty acid phytosterol ester according to any one of claims 1 to 9.

[0023] In some embodiments, the fatty acid phytosteryl ester is one of phytosteryl oleate, phytosteryl isostearate, phytosteryl isostearyl dimer linoleate, phytosteryl macadamia oleate, phytosteryl canola oleate, phytosteryl canola glycerides, phytosteryl / isostearyl / cetyl / stearyl / behenyl dimer linoleate, phytosteryl / behenyl / octyldodecanol lauroyl glutamate, phytosteryl / octyldodecanol lauroyl glutamate, bis-behenyl / phytosteryl dimer linoleyl dimer linoleate.

[0024] A third aspect of the present application provides a cosmetic, comprising a fatty acid phytosterol ester prepared by the method for preparing a fatty acid phytosterol ester according to any one of claims 10 to 11.

[0025] In the preparation method of fatty acid phytosterol esters, fatty acid phytosterol esters and cosmetics provided in the embodiments of the present application, by using a catalytically effective amount of dodecylbenzene sulfonic acid, it is possible to reduce the esterification reaction temperature while maintaining the reaction rate of fatty acids and phytosterols, avoid or reduce the oxidation discoloration and coking of the product fatty acid phytosterol esters due to excessively high temperature, and improve the quality of fatty acid phytosterol esters. DETAILED DESCRIPTION

[0026] In order to make the invention purpose, technical scheme and beneficial technical effect of the present application clearer, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the embodiments described in this specification are only for explaining the present application, not for limiting the present application.

[0027] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unambiguous range; and any lower limit can be combined with other lower limits to form an unambiguous range, and any upper limit can be combined with any other upper limit to form an unambiguous range. In addition, although not explicitly stated, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unambiguous range.

[0028] In the description herein, when a composition is described as containing, comprising or including specific components, or when a process is described as containing, comprising or including specific process steps, it is expected that the composition of the present application also consists essentially of or consists of the components, and the process of the present application also consists essentially of or consists of the process steps.

[0029] The use of the terms "including," "comprising," "containing," and "having" should generally be interpreted as open ended and non-limiting unless expressly stated otherwise.

[0030] In the description of this article, it should be noted that, unless otherwise specified, “above” and “below” are inclusive of the number itself, and the “multiple” in “one or more” means more than two.

[0031] The above-mentioned summary of the invention of the present application is not intended to describe each disclosed embodiment or each implementation in the present application. The following description more specifically illustrates exemplary embodiments. In many places throughout the application, guidance is provided by a series of examples, which can be used in various combinations. In each example, enumeration is only used as a representative group and should not be interpreted as exhaustive.

[0032] Phytosterol esters can replace lanolin as a cosmetic raw material. Phytosterol esters can delay the penetration of water through the epidermis and increase the moisture content of the skin. Phytosterol esters also have a high refractive index, which can bring gloss to cosmetics. In the related art, phytosterol esters are prepared by phytosterols and fatty acids, and catalysts are introduced to speed up the reaction. The introduced catalysts include sodium methoxide, dichlorothionyl, copper nitrate, etc. The introduced catalysts are corrosive and toxic, making the prepared phytosterol esters unfavorable for use as raw materials for cosmetics. In the related art, phytosterols and fatty acids are maintained at 150°C to 200°C to prepare phytosterol esters, which not only consumes a lot of energy, but also causes oxidation and discoloration of the oil, and even coking.

[0033] A first aspect of the present application provides a method for preparing fatty acid phytosterol esters, the method comprising:

[0034] In the presence of a catalytically effective amount of dodecylbenzenesulfonic acid, fatty acids and alcohol compounds are esterified to generate fatty acid phytosterol esters, wherein the alcohol compounds include phytosterols.

[0035] In the present application, "catalytically effective amount" means an amount of the catalyst sufficient to cause esterification of fatty acids and alcohol compounds.

[0036] The alcohol compound includes at least phytosterols, and the alcohol compound may also include other alcohols in addition to phytosterols according to the desired prepared fatty acid phytosterol esters. For example, when the fatty acid phytosterol esters are phytosterol / isostearyl alcohol / cetyl alcohol / stearyl alcohol / behenyl alcohol dimer linoleate, the alcohol compound includes phytosterols, behenyl alcohol, stearyl alcohol, isostearyl alcohol and cetyl alcohol.

[0037] Dodecylbenzenesulphonic acid is a light yellow to brown viscous substance. Dodecylbenzenesulphonic acid can be used as a catalyst to catalyze the esterification reaction between fatty acids and alcohol compounds to generate fatty acid phytosterol esters, thereby achieving a reduction in the esterification reaction temperature while maintaining the reaction rate of fatty acids and phytosterols. When fatty acids and alcohol compounds undergo esterification, dodecylbenzenesulphonic acid can be used not only as a catalyst but also as a surfactant. The water generated by the reaction is encapsulated in the oil phase, promoting the forward reaction and weakening the reversibility of the esterification reaction.

[0038] In the preparation method of fatty acid phytosterol esters provided in the present application, by using a catalytically effective amount of dodecylbenzene sulfonic acid, it is possible to lower the esterification reaction temperature while maintaining the reaction rate of fatty acids and phytosterols, thereby avoiding or reducing the oxidation discoloration and coking of the product fatty acid phytosterol esters due to excessively high temperature, thereby improving the quality of fatty acid phytosterol esters, especially the quality of the prepared fatty acid phytosterol esters used as raw materials for cosmetics.

[0039] In some embodiments, the method for preparing fatty acid phytosterol esters comprises:

[0040] S100, providing a mixture of fatty acids and alcohol compounds;

[0041] S200, adding a catalytically effective amount of dodecylbenzene sulfonic acid to the mixture, using the dodecylbenzene sulfonic acid as a catalyst to catalyze an esterification reaction between fatty acids and phytosterols to obtain fatty acid phytosterol esters, and the esterification reaction temperature is 80°C to 120°C.

[0042] In S100, fatty acids and alcohol compounds are directly mixed without introducing other solvents into the mixture, thereby avoiding unwanted side reactions of the solvent during the process of generating fatty acid phytosterol esters, and avoiding solvent residues in the prepared fatty acid phytosterol esters, thereby affecting the quality of the prepared fatty acid phytosterol esters.

[0043] When the esterification reaction temperature is set below 80°C and no other solvents are introduced, the fatty acids are in a solid state, resulting in uneven reaction of phytosterols and fatty acids, making it difficult to control the esterification reaction. When the esterification reaction temperature is set above 120°C, the product fatty acid phytosterol esters are prone to oxidation, discoloration, and coking, which is not conducive to the use of the prepared fatty acid phytosterol esters as raw materials for cosmetics. Therefore, when dodecylbenzenesulfonic acid is used as a catalyst, the esterification reaction temperature is set to 80°C to 120°C, and each reactant can be fully melted, which is conducive to improving the uniformity of the reaction of phytosterols and fatty acids, increasing the reaction rate, and avoiding or reducing the oxidation, discoloration, and coking of the prepared fatty acid phytosterol esters.

[0044] Optionally, the esterification reaction temperature is set to 80°C to 100°C, 80°C to 110°C, 90°C to 100°C, 90°C to 120°C, or 100°C to 120°C.

[0045] Optionally, fatty acids and phytosterols are placed in a reaction container for esterification reaction, and the reaction container is heated to reach the desired esterification reaction temperature in the reaction container. The reaction container can be a three-mouth reaction spherical bottle, one of which is connected to a temperature sensor, one is connected to a physical stirrer, and one is connected to a condenser. Optionally, the internal temperature of the reaction container is 110°C and the external temperature is 120°C. Optionally, the internal temperature of the reaction container is 100°C and the external temperature is 110°C.

[0046] In some embodiments, in S200, dodecylbenzene sulfonic acid is used as a catalyst to catalyze the esterification reaction of fatty acids and phytosterols to obtain fatty acid phytosterol esters, including:

[0047] S210, esterification reaction of fatty acid and phytosterol at a first temperature T1 and a first pressure P1 to obtain fatty acid phytosterol ester;

[0048] S220, distilling the fatty acid phytosterol ester at a second temperature T2 and a second pressure P2 to purify the fatty acid phytosterol ester;

[0049] Among them, T1, T2∈[80℃~120℃], P1>P2, P2<101.325kPa.

[0050] The first temperature T1 and the second temperature T2 may be the same or different, but T1, T2∈[80°C~120°C], that is, the reactants and products are kept at 80°C~120°C to avoid the reactants and products from being overcooled and solidified, or overheated and oxidized.

[0051] The standard atmospheric pressure is 101.325 kPa, P1>P2, P2<101.325 kPa, that is, fatty acids and phytosterols first undergo esterification reaction under the first atmospheric pressure P1, and the esterification reaction is completed after the first reaction time t1; the reaction vessel is decompressed to reduce the boiling point of each compound in the reaction vessel, and distilled for the second time t2, so that part of the compounds can be discharged by controlling the second temperature T2 and the boiling point of each compound to purify the fatty acid phytosterol esters.

[0052] The water content in the prepared fatty acid phytosterol ester increases, which will lead to an increase in the melting point of the prepared fatty acid phytosterol ester, so that when the cosmetics prepared using the fatty acid phytosterol ester as a raw material are heated, oil particles are easily generated, affecting the use of cosmetics. When fatty acids and alcohol compounds are subjected to esterification, water is generated. By maintaining the fatty acid phytosterol ester prepared in S210 at a second temperature T2 and a second air pressure P2 for distillation, at the second air pressure P2, the boiling point of water is higher than or equal to the second temperature T2, then part or all of the water in the fatty acid phytosterol ester can be discharged by distillation, reducing the water content in the fatty acid phytosterol ester. Esterification and reduced pressure distillation can be carried out in the same reaction vessel to simplify the preparation steps.

[0053] Therefore, by distilling the fatty acid phytosterol esters at the second temperature T2 and the second air pressure P2 for the second time period t2, part or all of the water, dodecylbenzene sulfonic acid, and free small molecule fatty acids can be removed to purify the fatty acid phytosterol esters.

[0054] In some embodiments, according to the acid value and color of the fatty acid phytosterol ester prepared in S210, the second temperature T2, the second air pressure P2 and the second duration t2 are determined so that the purified fatty acid phytosterol ester is less than the target acid value. Wherein, the acid value is proportional to the second temperature T2, the smaller the acid value, the smaller the numerical value of the second temperature T2, the larger the acid value, the larger the numerical value of the second temperature T2. The acid value is inversely proportional to the second air pressure P2, the smaller the acid value, the larger the numerical value of the second air pressure P2, the larger the acid value, the smaller the numerical value of the second air pressure P2. The acid value is inversely proportional to the second duration t2, the smaller the acid value, the larger the numerical value of the second duration t2, the larger the acid value, the smaller the numerical value of the second duration t2. The target acid value can be 3.

[0055] In some embodiments, under the second gas pressure P2, the boiling point of dodecylbenzene sulfonic acid is B1, and the boiling point of fatty acid phytosterol ester is B2, B2≥T2≥B1, that is, distillation is performed while maintaining the second temperature T2 and the second gas pressure P2. Since the boiling point B2 of fatty acid phytosterol ester is not reached, the boiling point B1 of dodecylbenzene sulfonic acid is reached, thereby the dodecylbenzene sulfonic acid in the fatty acid phytosterol ester can be discharged.

[0056] In some embodiments, the fatty acid and the phytosterol undergo an esterification reaction at the first temperature T1 and the first pressure P1 until the acid value is less than or equal to 3, and S220 is executed.

[0057] In some embodiments, the fatty acid and the phytosterol are esterified at a first temperature T1 and a first pressure P1 for a first time period, and the first time period is 2 hours to 6 hours.

[0058] Optionally, the first time length t1 is 2 hours to 4 hours. The first time length t1 may specifically be 2 hours, 3 hours, 5 hours, etc. The first time length t1 may be shortened by physically stirring the fatty acids and the phytosterols.

[0059] In some embodiments, the fatty acid phytosterol esters are distilled at a second temperature T2 and a second pressure P2 for a second time period, wherein the second time period is 1 hour to 6 hours.

[0060] Optionally, the second time length t2 is 1 hour to 4 hours. The second time length t2 can be specifically 1 hour, 2 hours, 3 hours, 5 hours, etc. The second time length t2 can be reduced by increasing the second temperature T2 and reducing the second air pressure P2. The values ​​of the first time length t1 and the second time length t2 can be consistent or inconsistent.

[0061] In some embodiments, after S210 and before S220, the steps include:

[0062] When the acid value of the fatty acid phytosterol ester is less than a first preset acid value, sodium bicarbonate aqueous solution is added to neutralize the acid value of the fatty acid phytosterol ester to a second preset acid value, wherein the first preset acid value is less than the second preset acid value.

[0063] A 2% w / w sodium bicarbonate aqueous solution can be added to accelerate the neutralization efficiency. The added sodium bicarbonate can react with dodecylbenzene sulfonic acid to form sodium dodecylbenzene sulfonate. Sodium dodecylbenzene sulfonate is a widely used surfactant and is relatively safe for use in the preparation of cosmetics. Therefore, by adding sodium bicarbonate, the catalyst dodecylbenzene sulfonic acid is neutralized while reducing the acid value of the product fatty acid phytosterol ester.

[0064] Optionally, the first preset acid value is 10 mgKOH / g. The second preset acid value is 3 mgKOH / g.

[0065] In some embodiments, the mass of dodecylbenzenesulfonic acid is 0.1-1% w / w of the total mass of the fatty acid and the alcohol compound.

[0066] Optionally, the amount of the catalyst used in the present application is 0.1-0.5% w / w of the total weight of the fatty acid and alcohol compound, for example, 0.1-0.2% w / w, 0.1-0.3% w / w, 0.1-0.4% w / w.

[0067] The greater the amount of dodecylbenzenesulfonic acid, the higher the efficiency of the esterification reaction between fatty acids and alcohol compounds. Compared with the addition of dodecylbenzenesulfonic acid greater than 1% w / w, when the amount of dodecylbenzenesulfonic acid is set to 0.1-1% w / w, dodecylbenzenesulfonic acid can still provide higher catalytic activity.

[0068] The added dodecylbenzene sulfonic acid is 0.1-1% w / w, so that even if the dodecylbenzene sulfonic acid is not distilled out under the second gas pressure P2, the amount of dodecylbenzene sulfonic acid remaining in the generated fatty acid phytosterol ester is very small, thereby improving the use safety of the generated fatty acid phytosterol ester. On the basis of setting the dodecylbenzene sulfonic acid to 0.1-1% w / w, part or all of the dodecylbenzene sulfonic acid is distilled out under the second gas pressure P2, thereby further reducing the residual dodecylbenzene sulfonic acid in the prepared fatty acid phytosterol ester.

[0069] In some embodiments, in the fatty acid and alcohol compounds, the ratio of the number of hydroxyl groups to the number of carboxyl groups is (0.5-1.5): (0.5-1.5).

[0070] Fatty acids provide carboxyl groups, alcohol compounds provide hydroxyl groups, and carboxyl groups and hydroxyl groups undergo esterification reaction. Preferably, the ratio of the number of hydroxyl groups to carboxyl groups is (0.8-1.2):(0.8-1.2). For example: the ratio of the number of hydroxyl groups to carboxyl groups is 1:(0.8-1), 1:(0.8-0.9). The number of hydroxyl groups can be set to be more than the number of carboxyl groups to promote the esterification reaction. Compared with fatty acids, excess unreacted alcohol compounds have little effect on the acid value of the prepared fatty acid phytosterol esters.

[0071] In some embodiments, the phytosterol is one or a mixture of any proportion of sitosterol, stigmasterol, campesterol, and brassicasterol.

[0072] The phytosterols include a mixture of 40-50% sitosterol, 20-28% stigmasterol, 20-28% campesterol and 0.5-5% brassicasterol, based on the total weight of the phytosterols.

[0073] In some embodiments, the fatty acid is a mixture of any proportion of one or more of fatty acids having 8 to 36 carbon atoms, polymerized fatty acids, and aliphatic amino acids.

[0074] The fatty acid can be a straight chain fatty acid or a branched chain fatty acid containing a carbon chain of C8 or more carbon atoms, such as C8 or more carbon atom alcohol, C10 or more carbon atom acid and C12 or more carbon atom alcohol. The fatty acid is selected from one or more of hexanoic acid, octanoic acid, lauric acid, palmitic acid, oleic acid, dimerized linoleic acid, isostearic acid or lauroyl glutamic acid.

[0075] Oleic acid can be obtained by chemical synthesis, or can be oleic acid extracted from macadamia nut oil, oleic acid extracted from rapeseed oil, or oleic acid extracted from any other extract.

[0076] A second aspect of the embodiment of the present application provides a fatty acid phytosterol ester, which is prepared by the aforementioned preparation method of fatty acid phytosterol ester.

[0077] In some embodiments, the fatty acid phytosteryl ester is one of phytosteryl oleate, phytosteryl isostearate, phytosteryl isostearyl dimer linoleate, phytosteryl macadamia oleate, phytosteryl canola oleate, phytosteryl canola glycerides, phytosteryl / isostearyl / cetyl / stearyl / behenyl dimer linoleate, phytosteryl / behenyl / octyldodecanol lauroyl glutamate, phytosteryl / octyldodecanol lauroyl glutamate, bis-behenyl / phytosteryl dimer linoleyl dimer linoleate.

[0078] A second aspect of the embodiments of the present application provides a cosmetic comprising phytosterol fatty acid esters prepared by the aforementioned method for preparing phytosterol fatty acid esters.

[0079] Cosmetics include color makeup products and skin care products. Color makeup products include lipstick, foundation, blush, etc., and skin care products include moisturizer, essence, conditioner, etc.

[0080] Example

[0081] The following examples describe the disclosure of the present invention in more detail, and these examples are intended for illustrative purposes only, as various modifications and variations within the scope of the disclosure of the present invention will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further processing, and the instruments used in the examples are commercially available.

[0082] Examples 1-10

[0083] Please refer to Table 1 for setting Examples 1-10. Add fatty acids and alcohol compounds to a 3L three-necked reaction spherical bottle, and then add 0.1-1% w / w of the total mass of the catalyst dodecylbenzenesulfonic acid. Replace the gas in the reaction spherical bottle with vacuum-nitrogen three times, and carry out the esterification reaction at 80-120°C for the first time, which is 2-6 hours, and stir at 180rpm. After the first reaction time, stop heating and test the acid value of the reaction product.

[0084] Table 1

[0085]

[0086]

[0087] It can be seen from Table 1 that when dodecylbenzenesulfonic acid is 0.1-1% w / w, the fatty acids and alcohol compounds provided in Table 1 can undergo esterification reaction at 80-120°C, and the esterification reaction can be partially or completely completed within 6 hours to generate the corresponding fatty acid phytosterol esters.

[0088] In the fatty acids and alcohol compounds of Examples 1-10, the ratio of carboxyl to hydroxyl is 0.8:1, and the hydroxyl is slightly excessive. When the reaction proceeds in the forward direction, all or most of the carboxyl groups react, and the acid value decreases. The acid value can be used as a characterization of the degree of esterification. It can be seen from the examples that a higher catalyst content, a higher temperature and a longer reaction time are conducive to the reaction. When the catalyst is 0.7-1% w / w, the reaction temperature is 100-120°C, and the first time is 3-6h, the acid value after the reaction is below 10, indicating a high degree of esterification.

[0089] With respect to Examples 5-10, the prepared phytosterol fatty acid esters were vacuum distilled at 82° C. for 2-6 h to purify the phytosterol fatty acid esters, and the acid value of the purified phytosterol fatty acid esters was tested.

[0090] Table 2

[0091]

[0092] It can be seen from Table 2 that after vacuum distillation purification of fatty acid phytosterol esters at 82°C for 2-4h, the acid value of the prepared fatty acid phytosterol esters can be reduced from less than 25mgKOH / g to less than 3mgKOH / g at most. Vacuum distillation purification can effectively reduce free small molecular fatty acids and water generated by the reaction, promote the forward esterification reaction, thereby showing a decrease in acid value and a further increase in the degree of esterification.

[0093] Examples 11-16 and Comparative Examples 1-4

[0094] Preparation of phytosterol / isostearyl alcohol / cetyl alcohol / stearyl alcohol / behenyl alcohol dimer linoleate. 1N phytosterol (137g), 1N C22 behenyl alcohol (108g), 1.2N C18 stearyl alcohol (108g), 0.3N C18 isostearyl alcohol (26.6g), 0.5N C16 cetyl alcohol (40.3g), 1.6N dimer linoleic acid (298g) were mixed, wherein the sum of the hydroxyl equivalents was 4N, the carboxyl equivalent was 3.2N, and the ratio of hydroxyl to carboxyl was 1:0.8. The mixture was added to a 3L three-necked reaction spherical bottle, and then dodecylbenzene sulfonic acid was added according to the catalyst content in Table 3. After more than three vacuum-nitrogen replacements, the spherical bottle was heated under nitrogen, and the reactants were stirred at 180 rpm to perform the first stage of esterification until the reaction time was reached. The acid value of the fatty acid phytosterol ester produced in each embodiment was detected to be 1, and then the second stage of vacuum distillation reaction was performed, and then the acid value of the fatty acid phytosterol ester purified in each embodiment was detected to be 2 and the color at room temperature.

[0095] Table 3

[0096]

[0097] It can be seen from Examples 11-12 and Comparative Examples 1-2 in Table 3 that when the dosage of dodecylbenzenesulfonic acid is 0.01-2w / w, the esterification rate calculated by the acid value 1 increases with the increase in the dosage of dodecylbenzenesulfonic acid, indicating that the increase in the dosage of dodecylbenzenesulfonic acid can increase the esterification reaction rate of fatty acids and alcohol compounds. When the dosage of dodecylbenzenesulfonic acid is less than 0.1%w / w, the esterification rate is low, which is not conducive to the production of fatty acid phytosterol esters; when the dosage of dodecylbenzenesulfonic acid is greater than 1%w / w, the color of the prepared fatty acid phytosterol esters becomes darker. Therefore, selecting the dosage of dodecylbenzenesulfonic acid to be greater than or equal to 0.1%w / w and less than 1%w / w can ensure that the esterification reaction rate of fatty acids and alcohol compounds is at an appropriate level, and the color is light, which is conducive to direct use as a raw material for preparing cosmetics.

[0098] It can be seen from Examples 13-15 and Comparative Example 3 in Table 3 that the esterification rate increases with the increase of the esterification reaction temperature, indicating that the increase in the amount of dodecylbenzene sulfonic acid can increase the esterification reaction rate of fatty acids and alcohol compounds. When the esterification reaction temperature is less than 80°C, the esterification rate is low, which is not conducive to the production of fatty acid phytosterol esters. When the esterification reaction temperature is increased to more than 120°C, the risk of product oxidation will be increased, resulting in the product color becoming darker and having an oxidized grease odor, and the prepared fatty acid phytosterol esters cannot be used as raw materials to prepare cosmetics. Therefore, the esterification reaction temperature is selected to be 80°C to 120°C, which can ensure that the esterification reaction rate of fatty acids and alcohol compounds is at an appropriate level, and the generated fatty acid phytosterol esters are not easily oxidized.

[0099] It can be seen from Examples 16-17 and Comparative Example 4 in Table 3 that the first time and the second time are within 3-8 hours, and the esterification rate increases with the increase of the reaction time, indicating that increasing the reaction time within a certain range can increase the esterification rate of fatty acids and alcohol compounds, which is conducive to the full reaction of fatty acids and alcohol compounds. When the first time and the second time exceed 6 hours, the color of the reactant deepens, which is not conducive to direct use and requires additional decolorization and purification steps.

[0100] Embodiment 18

[0101] Preparation of phytosterol / isostearyl alcohol / cetyl alcohol / stearyl alcohol / behenyl alcohol dimer linoleate. 1N phytosterol (137g), 1N C22 behenyl alcohol (108g), 1.2N C18 stearyl alcohol (108g), 0.3N C18 isostearyl alcohol (26.6g), 0.5N C16 cetyl alcohol (40.3g), 1.6N dimer linoleic acid (298g) were mixed, wherein the sum of the hydroxyl equivalents was 4N, the carboxyl equivalent was 3.2N, and the ratio of hydroxyl to carboxyl was 1:0.8. The mixture was added to a 3L three-necked reaction flask, and 1.8g (0.25% w / w) of dodecylbenzenesulfonic acid as a catalyst was added. The flask was heated to an internal temperature of 100°C under a nitrogen atmosphere for more than three times, and the reactants were stirred at 180 rpm for esterification reaction for 3 hours; the pressure was reduced to 0.01 mbar and distilled for 3 hours, and the internal temperature was 110°C. The final product was a yellow-white waxy solid at room temperature, with an acid value of 0.23. The quantitative liquid chromatography characterization showed that the esterification rate was 95% based on phytosterols, as the reaction was cross-esterification.

[0102] The above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A method for preparing fatty acid phytosterol esters, characterized in that: The method comprises: Fatty acids and alcohol compounds are esterified in the presence of a catalytically effective amount of dodecylbenzenesulfonic acid to generate fatty acid phytosterol esters, wherein the alcohol compounds include phytosterols.

2. The method for preparing phytosterol fatty acid esters according to claim 1, characterized in that: The method comprises: Providing a mixture of the fatty acid and the alcohol compound; A catalytically effective amount of dodecylbenzenesulfonic acid is added to the mixture. The dodecylbenzenesulfonic acid acts as a catalyst to catalyze the esterification reaction between the fatty acid and the phytosterol to obtain fatty acid phytosterol esters. The esterification reaction temperature is 80°C to 120°C.

3. The method for preparing phytosterol fatty acid esters according to claim 2, characterized in that: The dodecylbenzenesulfonic acid is used as a catalyst to catalyze the esterification reaction between the fatty acid and the phytosterol to obtain fatty acid phytosterol esters, including: The fatty acid and the phytosterol undergo esterification reaction at a first temperature T1 and a first pressure P1 to obtain fatty acid phytosterol esters; distilling the fatty acid phytosterol ester at a second temperature T2 and a second gas pressure P2 to purify the fatty acid phytosterol ester; Among them, T1, T2∈[80℃~120℃], P1>P2, P2<101.325kPa.

4. The method for preparing phytosterol fatty acid esters according to claim 3, characterized in that: The fatty acid and the phytosterol are esterified at a first temperature T1 and a first pressure P1 for a first time period, wherein the first time period is 2 hours to 6 hours.

5. The method for preparing phytosterol fatty acid esters according to claim 3, characterized in that: The fatty acid phytosterol ester is distilled at a second temperature T2 and a second gas pressure P2 for a second time period, wherein the second time period is 1 hour to 6 hours.

6. The method for preparing phytosterol fatty acid esters according to claim 4, characterized in that: After the fatty acid and the phytosterol are subjected to an esterification reaction at a first temperature T1 and a first pressure P1 to obtain fatty acid phytosterol esters, the fatty acid phytosterol esters are distilled at a second temperature T2 and a second pressure P2, and before the fatty acid phytosterol esters are purified, the preparation method further comprises: When the acid value of the fatty acid phytosterol ester is less than a first preset acid value, sodium bicarbonate is added to neutralize the acid value of the fatty acid phytosterol ester to a second preset acid value, and the first preset acid value is greater than the second preset acid value.

7. The method for preparing phytosterol fatty acid esters according to claim 1, characterized in that: The mass of the dodecylbenzenesulfonic acid is 0.1-1% w / w of the total mass of the fatty acid and the alcohol compound.

8. The method for preparing phytosterol fatty acid esters according to claim 1, characterized in that: In the fatty acid and the alcohol compound, the quantity ratio of hydroxyl group to carboxyl group is (0.5-1.5):(0.5-1.5).

9. The method for preparing phytosterol fatty acid esters according to claim 1, characterized in that: The phytosterol is one of sitosterol, stigmasterol, campesterol, and brassicasterol, or a mixture of any proportion of the above; The fatty acid is a mixture of one or more of fatty acids with 8 to 36 carbon atoms, polymerized fatty acids, and aliphatic amino acids in any proportion.

10. A fatty acid phytosterol ester, characterized in that: The fatty acid phytosterol ester is prepared by the preparation method of fatty acid phytosterol ester according to any one of claims 1-9.

11. The phytosterol fatty acid ester according to claim 10, characterized in that The fatty acid phytosterol ester is one of phytosterol oleate, phytosterol isostearate, phytosterol isostearyl dimer linoleate, phytosterol macadamia oleate, phytosterol canola oleate, phytosterol canola oil glyceride, phytosterol / isostearyl alcohol / cetyl alcohol / stearyl alcohol / behenyl alcohol dimer linoleate, phytosterol / behenyl alcohol / octyldodecanol lauroyl glutamate, phytosterol / octyldodecanol lauroyl glutamate, di-behenyl alcohol / phytosterol dimer linoleate, and di-behenyl alcohol / isostearyl alcohol / phytosterol dimer linoleyl dimer linoleate.

12. A cosmetic, characterized in that: The cosmetic comprises phytosterol fatty acid ester prepared by the method for preparing phytosterol fatty acid ester according to any one of claims 10-11.

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