A sorbitan ester additive-free preservative sorbitan monoisopalmitate substitute, sorbitan mono(2-propyl)heptanoate, and a synthesis method thereof

Abstract

The present application provides a kind of sorbitan ester antiseptic additive-free replacement sorbitan monoisopropyl adipate and its synthesis method, with sorbitol, 2-propyl heptanoic acid as raw material, by one-step reaction to obtain the target product sorbitan monoisopropyl adipate. By characterizing its sterilization, washing and emulsification, etc. The results show that the preservative and bacteriostatic performance of sorbitan monoisopropyl adipate reaches and is better than the level of currently marketed sorbitan ester, can replace sorbitan ester, and has good emulsification, washing function. The synthesized sorbitan monoisopropyl adipate is used in detergent, can replace part of traditional surfactant, through decontamination power evaluation and microbial test, the washing effect is good, the detergent after replacement does not need to add conventional preservative, can pass microbial challenge test.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fine organic synthesis, and particularly relates to a sorbitan ester replacement product sorbitan monoisopropyl adipate and a synthesis method thereof. BACKGROUND

[0002] Sorbitan ester is a new functional daily chemical additive proposed by Clariant in 2010, and is also an important representative of the non-additive preservative. In cosmetics and washing and cleaning products, sorbitan ester can be used as a water-soluble solvent, an emulsifying agent and a preservative, and the like. In particular, the synergistic effect of sorbitan ester and other traditional preservatives is used in daily chemical product systems, so that the addition amount of the traditional preservative can be greatly reduced, the toxicity is significantly reduced, and the preservative capacity of the cosmetic product is more effective and safe. However, due to the large minimum inhibitory concentration value of sorbitan ester, the high price and the large addition amount, the use of sorbitan ester is limited.

[0003] At present, only Clariant produces sorbitan ester. Due to the great technical difficulty and the secrecy of the synthesis technology, there are few reports on the synthesis of sorbitan ester in domestic and foreign literatures. Li Chengbei et al. use sorbitol and octanoic acid as raw materials, and synthesize sorbitan ester with a monoglyceride content of 47.6% under nitrogen protection by using the method of etherification and esterification. The monoglyceride content of the product is 10% higher than that of the Clariant product. The above process needs to be carried out under nitrogen protection conditions through two-step reaction, and has defects such as complex reaction process, difficult catalyst treatment, serious pollution and complex operation, which greatly limits the popularization and use of sorbitan ester as a new multifunctional additive in the cosmetics and daily chemical industry. SUMMARY

[0004] In order to solve the defects such as complex process, difficult catalyst treatment, serious pollution and complex operation in the synthesis process of the non-additive preservative sorbitan ester, the application provides a sorbitan ester replacement product sorbitan monoisopropyl adipate, and provides a one-step synthesis method of sorbitan monoisopropyl adipate.

[0005] The structural formula of the non-additive preservative sorbitan ester replacement product sorbitan monoisopropyl adipate provided by the application is as follows:

[0006]

[0007] The synthesis method of the sorbitan mono(2-propyl) heptyl ester is as follows: sorbitol, 2-propyl heptanoic acid and a catalyst are sequentially added in a flask equipped with a thermometer, a stirrer, a condenser and a negative pressure device under stirring, the pressure of the system is controlled to be 4000-20000 Pa after the addition is completed, the temperature is increased to 200-230 DEG C, the reaction time is 4-6 hours, and the crude sorbitan mono(2-propyl) heptyl ester is obtained after the reaction is completed; the crude sorbitan mono(2-propyl) heptyl ester is subjected to molecular distillation to obtain a high-content sorbitan mono(2-propyl) heptyl ester product. The synthesis equation is as follows:

[0008]

[0009] In the synthesis method, the molar ratio of the sorbitol to the 2-propyl heptanoic acid is preferably 1:1.0-2.2.

[0010] In the synthesis method, the catalyst is a caustic alkali, preferably any one or a mixture of two of sodium hydroxide and potassium hydroxide, and the catalyst is further preferably added in an amount of 1%-2% of the mass of the 2-propyl heptanoic acid.

[0011] In the synthesis method, the distillation pressure of the molecular distillation is preferably 50-80 Pa, and the distillation temperature is preferably 110-130 DEG C.

[0012] The present application uses natural raw materials sorbitol and 2-propyl heptanoic acid as raw materials to synthesize sorbitan mono(2-propyl) heptyl ester through one-step reaction. Sorbitol is a sugar alcohol that can be metabolized by human body and belongs to a very widely sourced chemical raw material, which is widely used in food, daily chemical and pharmaceutical industries. 2-propyl heptanoic acid can be directly oxidized from 2-propyl heptanol, which is a byproduct of coal-to-olefin (MTO) process, and the domestic production capacity reaches nearly 500,000 tons / year, and the selling price is not high. Compared with the prior art, the present application has the following beneficial effects:

[0013] (1) The present application uses renewable natural raw material sorbitol and 2-propyl heptanoic acid, which is a byproduct of coal-to-olefin process, as raw materials, the raw materials are easy to obtain and widely sourced, the one-step synthesis process is simple and economical, the whole reaction conforms to the requirements of green and environmental protection, meets the development trend of "green chemical industry", and is suitable for industrialized large-scale production.

[0014] (2) The sorbitan mono(2-propyl) heptyl ester provided by the present application has a structure similar to that of sorbitan ester, and the bacteriostatic, washing and emulsifying functions thereof are characterized. The results show that the preservative and bacteriostatic performance of the sorbitan mono(2-propyl) heptyl ester reaches and is superior to that of the currently marketed sorbitan ester, and the sorbitan mono(2-propyl) heptyl ester can replace the sorbitan ester for use and has good washing and emulsifying functions, and can completely replace the sorbitan ester for use.

[0015] (3) The sorbitol mono(2-propyl)heptyl ester of the present invention has a low cost and can be directly applied to liquid detergents. It can replace the corresponding amount of active ingredients in liquid detergents with a dosage of 2% to 5%, and the detergency is comparable. It can pass the microbial challenge test without the need to add preservatives, thus ensuring the product's preservation requirements.

[0016] (4) This invention is of great significance for the transformation of my country’s high value-added preservative industry and narrowing the technological gap with the world’s leading companies in the industry. In particular, reducing the amount of traditional preservatives used or eliminating the use of traditional preservatives will be a revolutionary change in the preservative industry and will make an important contribution to human health. Attached Figure Description

[0017] Fig. 1 This is an HPLC chromatogram of crude sorbitol mono(2-propyl)heptyl ester prepared in Example 1.

[0018] Fig. 2 It is the dehydrated sorbitol mono(2-propyl)heptyl ester purified in Example 1. 1 HNMR image.

[0019] Fig. 3 This is an HPLC chromatogram of the dehydrated sorbitol mono(2-propyl)heptyl ester purified in Example 1. Detailed Implementation

[0020] To enable those skilled in the art to better understand and implement the technical solutions of the present invention, the present invention will be further described below with reference to specific embodiments and accompanying drawings. However, the embodiments described are not intended to limit the present invention. Unless otherwise specified, the experimental methods and detection methods described in the following embodiments are conventional methods; unless otherwise specified, the reagents and materials described are commercially available.

[0021] Example 1

[0022] In a flask equipped with a thermometer, stirrer, condenser, and a negative pressure device, 36.4 g (0.2 mol) of sorbitol, 37.84 g (0.22 mol) of 2-propylheptanoic acid, and 0.45 g (0.011 mol) of sodium hydroxide were added sequentially under stirring. After the addition was complete, the system pressure was controlled at 8000 Pa, the temperature was raised to 210 °C, and the reaction time was 4 hours. The acid value of the system was measured to be 8 mg KOH / g, yielding crude sorbitol mono(2-propyl)heptyl ester. The crude sorbitol mono(2-propyl)heptyl ester was then subjected to molecular distillation at a pressure of 60 Pa and a temperature of 120 °C to obtain a high-content sorbitol mono(2-propyl)heptyl ester product with a yield of 69.85% and a purity of 95.24%.

[0023] use 1HNMR, HPLC were used to characterize the structure and purity of the crude sorbitan mono(2-propyl) heptanoate and the sorbitan mono(2-propyl) heptanoate product, and the results are shown in Table 1. Figs. 1-3 The results show that the purity of the synthesized sorbitan mono(2-propyl) heptanoate can reach more than 95.0% after molecular distillation.

[0024] Example 2

[0025] In a flask equipped with a thermometer, a stirrer, a condenser, and a negative pressure device, 36.4 g (0.2 mol) of sorbitol, 72.24 g (0.42 mol) of 2-propyl heptanoic acid, and 1.3 g (0.023 mol) of potassium hydroxide were sequentially added under stirring. After completion of the addition, the pressure of the system was controlled at 4000 Pa, and the temperature was raised to 220°C. The reaction time was 5.5 hours, and the acid value of the system was 6 mgKOH / g. The crude sorbitan mono(2-propyl) heptanoate was obtained. The crude sorbitan mono(2-propyl) heptanoate was subjected to molecular distillation at a distillation pressure of 60 Pa and a distillation temperature of 120°C to obtain the sorbitan mono(2-propyl) heptanoate product with a high content, with a yield of 40.72% and a content of 93.08%.

[0026] Example 3

[0027] In a flask equipped with a thermometer, a stirrer, a condenser, and a negative pressure device, 36.4 g (0.2 mol) of sorbitol, 51.6 g (0.3 mol) of 2-propyl heptanoic acid, and 0.77 g (0.019 mol) of sodium hydroxide were sequentially added under stirring. After completion of the addition, the pressure of the system was controlled at 6000 Pa, and the temperature was raised to 220°C. The reaction time was 4.5 hours, and the acid value of the system was 9 mgKOH / g. The crude sorbitan mono(2-propyl) heptanoate was obtained. The crude sorbitan mono(2-propyl) heptanoate was subjected to molecular distillation at a distillation pressure of 60 Pa and a distillation temperature of 120°C to obtain the sorbitan mono(2-propyl) heptanoate product with a high content, with a yield of 55.46% and a content of 94.91%.

[0028] Example 4

[0029] In a flask equipped with a thermometer, a stirrer, a condenser, and a negative pressure device, 36.4 g (0.2 mol) of sorbitol, 61.92 g (0.36 mol) of 2-propyl heptanoic acid, and 0.93 g (0.017 mol) of potassium hydroxide were sequentially added under stirring, and after completion of the addition, the pressure of the system was controlled at 7000 Pa, and the system was heated to 210°C, and the reaction time was 5 hours, and the acid value of the system was detected to be 8 mgKOH / g, to obtain a crude sorbitan mono(2-propyl) heptanoate. The crude sorbitan mono(2-propyl) heptanoate was subjected to molecular distillation under the conditions of a distillation pressure of 60 Pa and a distillation temperature of 120°C to obtain a high-content sorbitan mono(2-propyl) heptanoate product at a yield of 51.70% and a content of 95.06%.

[0030] The properties of the sorbitan mono(2-propyl) heptanoate synthesized in the above example 1 and the commercially available sorbitan caprylate were compared and characterized, and the specific test values are shown in table 1. The bactericidal property was evaluated by the MIC value (agar dilution method), the emulsifying ability was evaluated by the water separation time method (soybean oil-water), and the detergency was determined by GB / T13174-2021 detergent for clothing and detergency and cyclic washing performance method.

[0031] Table 1 Comparison of properties of sorbitan mono(2-propyl) heptanoate and sorbitan caprylate

[0032]

[0033] The performance evaluation results of table 1 show that the MIC value of the sorbitan mono(2-propyl) heptanoate product synthesized in example 1 is less than that of the commercially available sorbitan caprylate, the emulsifying power and detergency value are greater than those of the sorbitan caprylate, proving that the antiseptic and bacteriostatic performance reaches and is superior to the level of the commercially available sorbitan caprylate, and has good emulsifying and washing functions.

[0034] Referring to GB / T 13174-2021, a standard laundry liquid (1# sample) was prepared, and 2% (2# sample) and 5% (3# sample) of sorbitan mono(2-propyl) heptanoate were used to replace the corresponding amount of active substances in the liquid detergent, as shown in table 2. According to GB / T13174-2021 detergent for clothing and detergency and cyclic washing performance, the detergency ratio of 2# and 3# laundry liquid samples was detected with the standard laundry liquid as the standard, and the results are shown in table 3.

[0035] Table 2 laundry liquid for experiment

[0036]

[0037] Table 3 washing experiment results

[0038]

[0039] The test results of Table 3 show that sorbitan mono(2-propyl)heptyl ester can replace part of the surfactant in the detergent, and has good decontamination power for the three kinds of contaminated cloth.

[0040] Microbial challenge test of laundry liquid containing sorbitan mono(2-propyl)heptyl ester: According to the USP (51) American Pharmacopoeia standard, the above prepared laundry liquid sample is subjected to a 28-day microbial challenge test, and 5 common bacteria are selected: Staphylococcus aureus; Escherichia coli; Pseudomonas aeruginosa; Candida albicans; Aspergillus niger. The microbial inhibition performance of the 5 samples in Example 3 is tested, and the test results are shown in Table 4.

[0041] Table 4 Microbial challenge experiment

[0042]

[0043] The test results of Table 4 show that the standard laundry liquid without adding preservatives cannot pass the microbial challenge experiment, and the laundry liquid using sorbitan mono(2-propyl)heptyl ester can pass the microbial challenge test without adding preservatives.

Claims

1. Use of sorbitan mono (2-propyl) heptanoate as a sorbitan octanoate substitute in a preservative, wherein the sorbitan mono (2-propyl) heptanoate is synthesized by the following method: sorbitol, 2-propyl heptanoic acid, a catalyst are sequentially added under stirring in a flask equipped with a thermometer, a stirrer, a condenser and connected to a negative pressure device, after the addition is completed, the pressure of the system is controlled at 4000-20000 Pa, the temperature is raised to 200-230℃, the reaction time is 4-6 hours, and sorbitan mono (2-propyl) heptanoate crude product is obtained, the sorbitan mono (2-propyl) heptanoate crude product is subjected to molecular distillation to obtain a high content of sorbitan mono (2-propyl) heptanoate product, the distillation pressure of the molecular distillation is 50-80 Pa, and the distillation temperature is 110-130℃; the synthesis equation is: the catalyst is any one or a mixture of both of sodium hydroxide and potassium hydroxide. The molar ratio of the sorbitol to 2-propyl heptanoic acid is 1:1.0-2.

2.

2. Use of sorbitan mono(2-propyl)heptanoate according to claim 1 as a replacement for sorbitan caprylate in a preservative, characterized in that: The catalyst addition amount is 1%-2% of the mass of the 2-propyl heptanoic acid.

3. Use of sorbitan mono(2-propyl)heptanoate according to claim 1 as a substitute for sorbitan caprylate in a preservative, characterized in that: ​

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