Malic acid diol ester, preparation method and application

Abstract

The invention provides malic acid glycol ester as well as a preparation method and application thereof, and relates to the field of organic synthesis. The molecular structural formula of the malic acid glycol ester is as follows: # imgabs0 #. The malic acid glycol ester disclosed by the invention can effectively reduce the irritation of cosmetics or skin cleansers to human skin or mucous membranes, and can further improve the touch feeling and the moisturizing performance on the basis of the performance of the diisostearyl alcohol malate; the preparation method of the malic acid glycol ester is short in synthetic route, easy to control the synthetic process, high in product yield, easy to obtain raw materials and beneficial to large-scale industrial production.

Description

Technical Field

[0001] The present invention relates to the field of organic synthesis, and particularly to a diol malate, a preparation method and an application thereof. Background Art

[0002] Reducing the irritation of cosmetics and skin cleansers to human skin or mucous membranes is a very important research direction. As is well known, many commonly used surfactants can cause irritation to human skin or mucous membranes. At the same time, some functional additive ingredients that are irritating to the human body will also be added to cosmetics or skin cleansers as needed, such as lower alcohols, pigments, fragrances, ultraviolet absorbers, peeling agents, and preservatives. In order to reduce the irritation caused by surfactants in cosmetics or skin cleansers, low-allergenic surfactants based on amino acids are disclosed in the prior art. For example, diisostearyl malate (CAS No.: 81230-05-9) is one of the commonly used oily matrices in cosmetics or skin cleansers. For a long time, as a representative component of high-viscosity and high-polarity oily matrices, it not only has certain safety and stability, but also has excellent gloss, affinity with pigments, and adhesiveness to human skin. Therefore, it is widely used as a base oil component of cosmetics or skin cleansers. In addition, diisostearyl malate can also be used in the fields of skin care and hair care to adjust the texture of products. However, traditionally used diisostearyl malate is considered to be an oil with relatively low viscosity, and its touch and moisturizing properties are not always satisfactory, and the relevant properties need to be further improved.

[0003] In the prior art, in order to improve the touch and moisturizing properties of the above diisostearyl malate, a diester composition of malic acid and by-products (such as isostearyl alcohol) from the manufacture of dimer acid has been disclosed. However, the use of diisostearyl malate as an irritation reliever (including conventional irritation relievers) is completely unknown.

[0004] Based on this, providing a novel malate that can effectively reduce the irritation of cosmetics or skin cleansers to human skin or mucous membranes and can further improve the touch and moisturizing properties on the basis of the performance of diisostearyl malate has important technical significance and research value. Summary of the Invention

[0005] To solve the technical problems existing in the prior art, the present invention provides a diol malate that can effectively reduce the irritation of cosmetics or skin cleansers to human skin or mucous membranes and can further improve the touch and moisturizing properties on the basis of the performance of diisostearyl malate; the present invention also provides a preparation method and an application of the diol malate.

[0006] To solve the above technical problems, the technical solutions adopted by the present invention are as follows: A diol malate, the molecular structural formula is as follows: .

[0007] A preparation method of the above-mentioned diol malate, comprising the following steps: the first reaction and the second reaction; The method of the first reaction is that in an inert gas environment, under alkaline conditions, in the presence of a catalyst, tetrahydrogeraniol undergoes a Guerbet reaction to obtain 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol; The method of the second reaction is that in a solvent environment, under the protection of an inert gas, 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol and DL-malic acid undergo an esterification reaction to prepare diol malate.

[0008] Preferably, in the first reaction, the temperature for the Guerbet reaction of tetrahydrogeraniol is 200 - 210 °C, and the reaction time is 2.5 - 3.5 h.

[0009] Preferably, in the first reaction, the catalyst is zinc oxide, and the added weight of zinc oxide is 0.04 - 0.06% of the weight of tetrahydrogeraniol.

[0010] Preferably, in the first reaction, sodium hydroxide is used to provide the alkaline condition, and the added weight of sodium hydroxide is 0.4 - 0.5% of the weight of tetrahydrogeraniol.

[0011] Preferably, in the second reaction, the molar ratio of 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol to DL-malic acid is 2 - 2.2:1.

[0012] Preferably, in the second reaction, the esterification reaction temperature is 100 - 120 °C, and the reaction time is 8 - 12 h.

[0013] An application of the above-mentioned diol malate in cosmetics or skin cleansers.

[0014] A cosmetic using the above-mentioned diol malate as an oily matrix or irritation reliever of the cosmetic.

[0015] A surfactant using the above-mentioned diol malate as an active ingredient or the main active ingredient.

[0016] Compared with the prior art, the beneficial effects of the present invention are: (1)The diol malate of the present invention, while having good basic properties, also has a very smooth smoothness, a viscous and comfortable feeling with extremely low viscosity, a very familiar skin familiarity. It feels comfortable when used on the skin surface, does not cause skin discomfort, can effectively reduce the irritation of cosmetics or skin cleansers to the human skin or mucous membranes, and can further improve the touch and moisturizing properties on the basis of the performance of diisostearyl malate. It is suitable for use as an oily matrix or irritation reliever for cosmetics.

[0017] (2)The preparation method of the diol malate of the present invention results in a diol malate with stable properties, a short synthesis route, an easily controllable synthesis process, a high product yield, and easily obtainable raw materials, which is conducive to large-scale industrial production.

[0018] (3)The diol malate of the present invention has an acid value of 0.28 mg KOH / g, a saponification value of 161 mg KOH / g, a hydroxyl value of 81 mg KOH / g, a refractive index (20 °C) of 1.465, a viscosity (25 °C) of 1610 mPa·s, and a maximum water absorption in an open environment of 20.6%. Description of the Drawings

[0019] Figure 1 It is the nuclear magnetic resonance hydrogen spectrum of the diol malate prepared in Example 2. Detailed Embodiments

[0020] For a clearer understanding of the technical features, objectives, and effects of the present invention, the specific embodiments of the present invention are now described. It should be noted that the following detailed descriptions are all exemplary and are intended to provide further explanations of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0021] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, "first", "second", etc. are used to distinguish similar objects and are not used to describe a specific order or sequence. In addition, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0022] An embodiment of the present invention provides a diol malate, and its molecular structural formula is as follows: .

[0023] An embodiment of the present invention also provides a preparation method for the aforementioned diol malate, including the following steps: the first reaction, the second reaction.

[0024] The method of the first reaction is as follows: in an inert gas environment, under alkaline conditions, in the presence of a catalyst, tetrahydrogeraniol undergoes a Guerbet reaction to obtain 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol.

[0025] In the first reaction, sodium hydroxide is used to provide an alkaline environment, and the added weight of sodium hydroxide is 0.4 - 0.5% of the weight of tetrahydrogeraniol.

[0026] In the first reaction, the catalyst is zinc oxide, and the added weight of zinc oxide is 0.04 - 0.06% of the weight of tetrahydrogeraniol.

[0027] In the first reaction, the reaction temperature for the Guerbet reaction of tetrahydrogeraniol is 200 - 210 °C, and the reaction time is 2.5 - 3.5 h.

[0028] Specifically, the method of the first reaction is as follows: in an inert gas environment, tetrahydrogeraniol, sodium hydroxide, and zinc oxide are mixed evenly, then heated to 200 - 210 °C, and after holding for a reflux reaction for 2.5 - 3.5 h, the solid matter is filtered off, and then impurities are removed by distillation to obtain 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol.

[0029] The method of the second reaction is as follows: in a solvent environment, under the protection of an inert gas, 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol and DL-malic acid undergo an esterification reaction to prepare diol malate.

[0030] In the second reaction, the molar ratio of 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol to DL-malic acid is 2 - 2.2:1.

[0031] In the second reaction, the esterification reaction temperature is 100 - 120 °C, and the esterification reaction time is 8 - 12 h.

[0032] Specifically, the method of the second reaction is as follows: 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol, DL-malic acid, and the solvent are mixed evenly, and under the protection of an inert gas, it is heated to 100 - 120 °C. After holding for an esterification reaction for 8 - 12 h, the unreacted DL-malic acid is removed by washing; then, it is concentrated and deodorized by steam to prepare diol malate.

[0033] The embodiment of the present invention also provides the application of the aforementioned diol malate in cosmetics or skin cleansers.

[0034] The embodiment of the present invention also provides a surfactant using the aforementioned diol malate as an active ingredient or the main active ingredient.

[0035] An embodiment of the present invention also provides a cosmetic product that uses the diol malate as an oily matrix or a stimulus reliever of the cosmetic product.

[0036] The following further describes the present invention in conjunction with some specific embodiments.

[0037] Example 1 This example provides the preparation of 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol (i.e., the first reaction): The specific preparation process route is as follows:

[0038] The specific preparation process is as follows: Add tetrahydrogeraniol (204 g, 1.29 mol), sodium hydroxide (1.00 g), and zinc oxide (0.113 g) into a reaction flask equipped with a water separator. Then, introduce nitrogen into the reaction flask and slowly heat it to 210 °C under nitrogen protection. After maintaining the temperature and refluxing for 3 h, filter to remove the solids, and then distill to remove the unreacted tetrahydrogeraniol and high-boiling impurities to obtain a colorless liquid, i.e., 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol (160 g, yield 42%).

[0039] Among them, adding sodium hydroxide provides an alkaline environment; zinc oxide acts as a catalyst to catalyze the reaction.

[0040] The nuclear magnetic resonance detection results of the 5,9-dimethyl-2-(6-methylheptan-2-yl)decan-1-ol prepared in this example are as follows: 1 H NMR(400MHz CDCl3) δ 3.64-3.51(m,2H),1.56-1.49(m,2H), 1.38-1.08(m,20H),0.86-0.84(m,18H).

[0041] Example 2 This example provides the preparation of diol malate (i.e., the second reaction): The specific preparation process route is as follows:

[0042] The specific preparation process is as follows: DL-malic acid (80 g, 0.579 mol), 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol (356 g, 1.193 mol), and heptane (80 g) as a solvent were charged into a 1 L reaction flask equipped with a stirrer, a thermometer, and a gas inlet tube; while introducing nitrogen, it was heated to 105 °C and kept reacting for 8 h; after the reaction was completed, the unreacted DL-malic acid was removed by washing with an aqueous sodium hydroxide solution, and the organic layer was concentrated; then, after steam deodorization under reduced pressure, a colorless oily liquid, namely diol malate (387 g, yield 93%), was obtained.

[0043] As Figure 1 shown, the nuclear magnetic resonance detection results of the diol malate prepared in this example were as follows: 1 H NMR (400 MHz, CDCl3) δ 5.25 (m, 1H), 4.56 (m, 2H), 4.11 (m, 2H), 2.73 (m, 1H), 2.65 (m, 1H), 1.80 (m, 2H), 1.62 (m, 5H), 1.25 - 1.19 (m, 36H), 0.97 - 0.81 (m, 36H).

[0044] Example 3 The acid value, saponification value, hydroxyl value, refractive index, viscosity, and the maximum water absorption in an open environment of the diol malate prepared in Example 2 were measured. At the same time, its usability was also evaluated using the following evaluation criteria: smoothness, stickiness, and familiarity to the skin when applied to the skin. The specific results are shown in the following table:

[0045] It can be seen that the diol malate prepared in the examples of the present invention has good basic properties, very smooth smoothness, a viscous and comfortable feeling with extremely low viscosity, a very familiar skin familiarity, a comfortable feeling when used on the skin surface, does not cause skin discomfort, can effectively reduce the irritation of cosmetics or skin cleansers to the human skin or mucous membranes, and can further improve the touch and moisturizing properties on the basis of the performance of diisostearyl malate, and is suitable for use as an oily matrix for cosmetics.

[0046] Unless otherwise specified, the percentages used in the present invention are all mass percentages.

[0047] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A diol malate, characterized in that, The molecular structural formula is as follows: 。 2. A method for preparing the diol malate as described in claim 1, characterized in that, It includes the following steps: The first reaction and the second reaction; The method of the first reaction is that in an inert gas environment, under alkaline conditions, in the presence of a catalyst, tetrahydrogeraniol undergoes the Guerbet reaction to obtain 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol; The method of the second reaction is that in a solvent environment, under the protection of an inert gas, 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol and DL-malic acid undergo an esterification reaction to prepare diol malate.

3. The preparation method of the diol malate according to claim 2, characterized in that, In the first reaction, the temperature for the Guerbet reaction of tetrahydrogeraniol is 200 - 210 °C, and the reaction time is 2.5 - 3.5 h.

4. The preparation method of the diol malate according to claim 2, wherein, In the first reaction, the catalyst is zinc oxide, and the added weight of zinc oxide is 0.04 - 0.06% of the weight of tetrahydrogeraniol.

5. The preparation method of the diol malate according to claim 2, characterized in that, In the first reaction, sodium hydroxide is used to provide the alkaline condition, and the added weight of sodium hydroxide is 0.4 - 0.5% of the weight of tetrahydrogeraniol.

6. The preparation method of the diol malate according to claim 2, characterized in that, In the second reaction, the molar ratio of 5,9-dimethyl-2-(6-methylheptan-2-yl)dec-1-ol to DL-malic acid is 2 - 2.2:

1.

7. The preparation method of diol malate according to claim 2, characterized in that, In the second reaction, the esterification reaction temperature is 100 - 120 °C, and the reaction time is 8 - 12 h.

8. Use of a diol malate as described in claim 1 in cosmetics or skin cleansers.

9. A cosmetic, characterized in that, Using the diol malate as described in claim 1 as an oily matrix or irritation reliever in cosmetics.

10. A surfactant, characterized in that, Using the diol malate as described in claim 1 as an active ingredient or the main active ingredient.

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