Narrow-distribution phytosterol EO / PO block polyether as well as preparation method and application thereof

Abstract

The invention provides narrow-distribution phytosterol EO / PO block polyether and a preparation method and application thereof.The phytosterol EO / PO block polyether is of a structure shown in the formula I. The phytosterol EO / PO block polyether is prepared through the following preparation method that under catalysis of a composite catalyst, natural phytosterol reacts with ethylene oxide and then reacts with epoxypropane, and the narrow-distribution phytosterol EO / PO block polyether is obtained. The phytosterol EO / PO block polyether is obtained; the composite catalyst comprises a main catalyst potassium hydroxide and an auxiliary catalyst triethanolamine. The phytosterol EO / PO block polyether provided by the invention has narrow molecular weight distribution, can balance the hydrophilicity and lipophilicity of the phytosterol, improves the performance stability of the phytosterol EO / PO block polyether, and expands the application field of the phytosterol.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of daily chemical raw materials, and mainly relates to a narrow-distribution phytosterol EO / PO block polyether and a preparation method and application thereof. BACKGROUND

[0002] With the rapid development of green chemical industry and functional materials, surfactants derived from natural raw materials have become popular products due to their environmental protection and functionality. Phytosterols, as natural steroidal compounds widely existing in plants, are generally considered to have mild performance, no toxicity and no irritation, good skin compatibility, and can reduce the irritation of formula products. Phytosterols are directly derived from natural plants and mainly exist in plant oils, legumes and cereal foods. Specifically, phytosterols are rich in plant oils such as corn germ oil, rapeseed oil, sesame oil, sunflower oil and olive oil, whole wheat flour, barley, millet, purple rice, corn flour, soybeans, green beans, black beans, mung beans, and vegetables such as cauliflower, carrots, beans and Chinese cabbage. Phytosterols have good antioxidant properties and physiological activity. Although phytosterols have been applied to a certain extent, their wide molecular weight distribution, high melting point, strong hydrophobicity and low solubility in aqueous systems limit their application range. In the present application, a composite catalyst is added to modify the block polymerization of natural phytosterols, EO and PO, so that the molecular weight distribution is narrowed, the hydrophilic EO segment and the lipophilic PO segment are introduced into the phytosterol molecular chain, the hydrophilic-lipophilic balance value is adjusted, and a series of non-ionic surfactants are obtained. The derivatives exhibit multiple application potential due to the modifiability of the molecular structure. This kind of surfactant not only retains the natural safety of phytosterols, but also obtains excellent surface activity through the regulation of EO and PO chains, thereby expanding the application field of phytosterols.

[0003] At present, the price of natural fatty alcohols is rising sharply, and the market demand for alcohols is increasing, so we add a composite catalyst to the phytosterols extracted from plant oils, legumes and cereals to study ethoxylation (EO) and propoxylation (PO), and obtain a preparation method of narrow-distribution phytosterol EO / PO block polyether, thereby alleviating the market supply of rising fatty alcohol prices and increasing alcohol demand.

[0004] The traditional EO / PO polymerization process uses a single catalyst (potassium hydroxide), and it is difficult to polymerize phytosterols, which has the problems of low reactivity, low conversion rate, and wide molecular weight distribution. The use of a single catalyst leads to a large amount of unreacted phytosterols and small molecule oligomers remaining in the product, with a purity of less than 90%. At the same time, chain transfer reactions easily occur during the reaction, resulting in a wide molecular weight distribution of the product, usually >1.5, which affects the performance stability of the product. Therefore, developing a method for preparing phytosterol EO / PO block polyether with narrow distribution has become a problem to be solved in the current industry. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a phytosterol EO / PO block polyether with narrow distribution, a preparation method thereof, and an application thereof. The phytosterol EO / PO block polyether product has high purity and good uniformity of molecular weight distribution, improves the performance stability of the phytosterol EO / PO block polyether, and expands the application field of phytosterols.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] On the one hand, the present application provides a phytosterol EO / PO block polyether, which has the following formula I structure:

[0008] ;

[0009] wherein R is the residue of phytosterol, m is the PO addition number, ranging from 1 to 10 (for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), and n is the EO addition number, ranging from 2 to 30 (for example, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, or 30, etc.).

[0010] Preferably, R is selected from the following groups:

[0011] 、 or .

[0012] The phytosterol EO / PO block polyether of the present application has a narrow molecular weight distribution, can balance the hydrophilic and lipophilic properties of phytosterols, improves the performance stability of the phytosterol EO / PO block polyether, and expands the application field of phytosterols.

[0013] On the other hand, the present application provides a preparation method of the phytosterol EO / PO block polyether as described above, which comprises the following steps:

[0014] Under the catalysis of a composite catalyst, natural phytosterols react with ethylene oxide, and then with propylene oxide to obtain the phytosterol EO / PO block polyether; the composite catalyst includes potassium hydroxide (KOH) as the main catalyst and triethanolamine (TEA) as the auxiliary catalyst.

[0015] In this invention, a composite catalyst consisting of potassium hydroxide (KOH) as the main catalyst and triethanolamine (TEA) as the auxiliary catalyst is used in the polymerization process of phytosterol EO / PO block polyethers. These two catalysts each play a different role. Triethanolamine is a tertiary amine compound with three hydroxyl groups. The hydroxyl functional groups of triethanolamine can provide acidic sites, while the amine functional groups can provide basic sites. By providing multiple active sites, triethanolamine promotes the reaction by regulating stereoselectivity. This allows it to form specific spatial structures with phytosterol molecules, restricting their reaction pathways and promoting specific reactions, thereby selectively generating the target product. Potassium hydroxide, a strong base, is used as the main base catalyst. Potassium hydroxide completely dissociates in water to produce hydroxide ions (OH-), providing a strongly alkaline reaction environment. The strong alkalinity of the catalyst can neutralize and promote ionization, thus facilitating the EO / PO block polymerization of phytosterols under alkaline conditions.

[0016] The combined use of triethanolamine and potassium hydroxide in the polymerization of phytosterol EO / PO block polyethers enhances the alkalinity of the main catalyst, potassium hydroxide, thereby increasing its catalytic activity, reaction rate, and selectivity. The application of triethanolamine as a co-catalyst in composite catalysts not only improves reaction rates but also alters the chemical properties and selectivity of the reaction. Furthermore, it helps the alkaline potassium hydroxide catalyst regulate the alkalinity and acidity of the reaction, inhibits chain transfer reactions, narrows the molecular weight distribution, and changes the selectivity of reactants. The synergistic effect of the two catalysts promotes the complete ethoxylation and propoxylation reactions, facilitating the formation of the target product.

[0017] Preferably, the mass ratio of potassium hydroxide (caustic soda flakes, KOH) to triethanolamine (TEA) is 1:0.3-0.5, which can be 1:0.3, 1:0.4, or 1:0.5, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable. Since adding solid potassium hydroxide is inconvenient, this invention uses a 50% aqueous solution of potassium hydroxide. Therefore, the ratio of the 50% potassium hydroxide solution to triethanolamine is 2:0.3-0.5.

[0018] Preferably, the amount of the composite catalyst added is 0.15%-0.3% of the mass of natural phytosterols, such as 0.15%, 0.175%, 0.2%, 0.225% or 0.3%.

[0019] Phytosterols are abundant in vegetable oils, legumes, and grains. In this invention, the phytosterol is selected from stigmasterol or β-sitosterol, or a mixture thereof, with a purity ≥95%, to ensure the purity of the initiator and reduce the interference of impurities on the polymerization reaction.

[0020] In this invention, ethylene oxide (EO) and propylene oxide (PO) can be industrial grade with a purity of ≥99.9% to avoid impurities affecting the reaction process.

[0021] Preferably, the natural phytosterols and the composite catalyst are dehydrated before the reaction.

[0022] Preferably, the dehydration process involves vacuum dehydration under a nitrogen atmosphere at a temperature of 130°C for 1-2 hours (e.g., 1 hour, 1.25 hours, 1.5 hours, 1.75 hours, or 2 hours), until the moisture content is ≤1%. This effectively removes trace amounts of moisture from natural plant sterols and prevents the reaction of moisture with EO and PO to produce byproducts such as ethylene glycol and propylene glycol, which could affect product purity.

[0023] Preferably, the molar ratio of the natural phytosterol to ethylene oxide is 1:2-30, such as 1:2, 1:4, 1:6, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:22, 1:24, 1:26, 1:28 or 1:30.

[0024] Preferably, the reaction temperature of the natural phytosterols with ethylene oxide is 150-160℃ (e.g., 150℃, 152℃, 155℃, 157℃ or 160℃, etc.), and the reaction time is 2-4 hours (e.g., 2 hours, 2.3 hours, 2.6 hours, 2.9 hours, 3.2 hours, 3.5 hours, 3.8 hours or 4 hours, etc.).

[0025] Preferably, the ethylene oxide is added to the reaction system dropwise.

[0026] Preferably, the dropping rate of the ethylene oxide is 0.5-1.0 mol / h (e.g., 0.5 mol / h, 0.57 mol / h, 0.64 mol / h, 0.71 mol / h, 0.78 mol / h, 0.85 mol / h, 0.92 mol / h, or 1 mol / h, etc.) to ensure the complete ethoxylation reaction of the phytosterols.

[0027] Preferably, the reaction of the natural phytosterols with ethylene oxide is carried out under nitrogen protection.

[0028] Preferably, the reaction of the natural phytosterols with ethylene oxide is carried out at a pressure ≤0.4 MPa (e.g., 0 MPa, 0.1 MPa, 0.2 MPa, 0.3 MPa, or 0.4 MPa). After the reaction is complete, the pressure is reduced to a constant value.

[0029] Preferably, the molar ratio of the natural phytosterol to propylene oxide is 1:1-10, such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0030] Preferably, the propylene oxide is added to the reaction system dropwise.

[0031] Preferably, the dropping rate of the propylene oxide is 0.3-0.8 mol / h (e.g., 0.3 mol / h, 0.4 mol / h, 0.5 mol / h, 0.6 mol / h or 0.8 mol / h, etc.).

[0032] In this invention, controlling the dropping rate of ethylene oxide and propylene oxide and maintaining the temperature during the reaction can prevent excessively high local concentrations of monomers (EO / PO) from causing explosive polymerization, while ensuring that the monomers (EO / PO) react fully with phytosterols and improving the conversion rate.

[0033] Preferably, the reaction temperature with propylene oxide is 150℃-160℃ (e.g., 150℃, 152℃, 155℃, 157℃ or 160℃, etc.), and the reaction time is 3-5 hours (e.g., 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, etc.).

[0034] Preferably, the reaction with propylene oxide is carried out under nitrogen protection.

[0035] Preferably, the reaction with propylene oxide is carried out at a pressure of ≤0.5MPa (e.g., 0MPa, 0.1MPa, 0.2MPa, 0.3MPa or 0.5MPa, etc.), and the pressure is reduced to a constant value after the reaction is completed.

[0036] Preferably, after the reaction with propylene oxide is completed, the temperature is lowered to 60-70°C (e.g., 60°C, 62°C, 65°C, 67°C, or 70°C), glacial acetic acid is added for neutralization, and the pH is 5.5-8 (e.g., 5.5, 6, 6.5, 7, or 8), and then low-boiling substances are removed under vacuum.

[0037] In this invention, acetic acid can neutralize residual catalyst, preventing residues from affecting the stability of the product.

[0038] In this invention, vacuum removal of low-boiling substances can effectively remove unreacted trace amounts of EO, PO and small molecule byproducts from phytosterol EO / PO block polyethers, thereby improving the purity of the product.

[0039] Preferably, the vacuum removal temperature for low-boiling substances is 90°C, the vacuum degree is ≤-0.098MPa (e.g., -0.098, -0.095, -0.01, -0.02 MPa, etc.), and the removal time is 1-1.5h.

[0040] In this invention, after removing low-boiling substances, the temperature is lowered to 70-80°C (e.g., 70°C, 72°C, 75°C, 78°C, or 80°C) before being discharged and packaged.

[0041] In this field, a single product structure is desired to obtain stable properties. However, the reaction of ethylene oxide, propylene oxide, and phytosterols yields a mixture of EO / PO addition numbers with different chain lengths. Therefore, in order to obtain polymers with relatively consistent chain lengths and uniform molecular weights, making their physical properties more stable and their applications more reliable, this invention provides a method for preparing EO / PO block polyethers of narrowly distributed phytosterols. The preparation method of this invention can obtain EO / PO block polyethers of narrowly distributed phytosterols.

[0042] The preparation method of this invention yields phytosterol EO / PO block polyethers with a purity ≥99%, reducing the interference of impurities on the application system; the molecular weight distribution coefficient (PDI) is ≤1.2, and the closer the distribution coefficient is to 1, the smaller the difference in molecular chain length in the phytosterol EO / PO block polyether product. The more uniform the molecular chain length, the more stable the physicochemical properties of the product and the smaller the batch-to-batch differences; the surface tension is 31-38 mN / m; the HLB value is 9-14, which can adapt to the emulsification requirements of different water-oil systems; it retains the characteristics of natural phytosterols, has good biocompatibility, and is suitable for cosmetics, food, and pharmaceutical fields.

[0043] On the other hand, the present invention provides the application of the phytosterol EO / PO block polyether as described above in cosmetics, food and pharmaceuticals.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] The phytosterol EO / PO block polyether of this invention has a purity of ≥99%, which can reduce the interference of impurities on the application system; the molecular weight distribution coefficient (PDI) is ≤1.2, the molecular weight distribution is narrow, the molecular chain length difference is very small, the molecular chain length is uniform, the product has relatively stable physicochemical properties, and the batch-to-batch difference is small; at 25°C, its surface tension is 31-38 mN / m; the HLB value is 9-14, which can adapt to the emulsification requirements of different water-oil systems; it retains the characteristics of natural phytosterols, has good biocompatibility, and is suitable for cosmetics, food and pharmaceutical fields. Detailed Implementation

[0046] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0047] Pretreatment Example 1

[0048] 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) were added to a 1000ML high-pressure reactor. After purging with nitrogen three times, the vacuum device was turned on to perform vacuuming. At the same time, the temperature was raised to 130℃ for moisture removal. Dehydration was carried out under vacuum (-0.098MPa) for 1 hour, and the moisture content was measured to be 0.94%.

[0049] Pre-processing Example 2

[0050] Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.2g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h, and the moisture content is measured to be 0.74%.

[0051] Pre-processing Example 3

[0052] Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydrate under vacuum (-0.098MPa) for 1 hour, and the moisture content is measured to be 1%.

[0053] Pre-processing Example 4

[0054] Add 100g of β-sitosterol with a purity ≥95% and 0.5g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000mL high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h, and the moisture content is measured to be 0.88%.

[0055] Pre-processing Example 5

[0056] 1. Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.20g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming operation. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1 hour, and the moisture content is measured to be 0.92%.

[0057] Pre-processing Example 6

[0058] 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) were added to a 1000ML high-pressure reactor. After purging with nitrogen three times, the vacuum device was turned on to perform vacuuming. At the same time, the temperature was raised to 130℃ for moisture removal. Dehydration was carried out under vacuum (-0.098MPa) for 1.5h, and the moisture content was measured to be 0.76%.

[0059] Pre-processing Example 7

[0060] Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydration is carried out under vacuum (-0.098MPa) for 1.5h, and the moisture content is measured to be 0.91%.

[0061] Pre-processing Example 8

[0062] Add 100g of stigmasterol with a purity ≥95% and 0.5g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming operation. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1 hour, and the moisture content is measured to be 0.98%.

[0063] As can be seen from preprocessing examples 1-8:

[0064] 1. The less mixed catalyst is added to natural phytosterols, the less water content and the higher the purity of natural phytosterols under the same removal time.

[0065] 2. When the same amount of mixed catalyst is added to natural phytosterols, the longer the removal time, the lower the water content and the higher the purity of the natural phytosterols. Therefore, this invention selected examples 2, 4, 6, and 7 (pretreatment examples with low water content) for the next reaction step.

[0066] Reaction Example 1

[0067] 1. Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.2g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.74%.

[0068] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0069] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0070] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0071] After testing: moisture content was 0.22%; solid content was 99.78%; number-average molecular weight was 1120; molecular weight distribution was 1.18; surface tension at 25℃ was 35 mN / m; HLB value was 12. Moisture and solid content tests were conducted according to GB / T11275-2007, with moisture content measured using the Karl Fischer volumetric method. Appendix A of GB / T11275-2007 explicitly includes methods for testing solid content. Surface tension was tested according to GB / T22237-2008, using the droplet method (drip method). The molecular weight test instrument was a Sephadex G-50 from Elite GPC (Shanghai).

[0072] Reaction Example 2

[0073] 1. Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.2g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.74%.

[0074] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (35 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (29 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0075] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0076] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0077] After testing: moisture content is 0.45%; solid content is 99.55%; number average molecular weight is 1130; molecular weight distribution is 1.16; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0078] Reaction Example 3

[0079] 1. Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.2g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.74%.

[0080] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0081] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0082] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0083] After testing: moisture content is 0.52%; solid content is 99.48%; number average molecular weight is 1110; molecular weight distribution is 1.2; surface tension at 25℃ is 36 mN / m; HLB value is 13.

[0084] Reaction Example 4

[0085] 1. Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.2g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.74%.

[0086] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0087] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0088] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0089] After testing: moisture content is 0.47%; solid content is 99.53%; number average molecular weight is 1130; molecular weight distribution is 1.16; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0090] Reaction Example 5

[0091] 1. Add 100g of stigmasterol with a purity ≥95% and 0.25g of composite catalyst (including 0.2g of potassium hydroxide solution (50%) and 0.05g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.74%.

[0092] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0093] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0094] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0095] After testing: moisture content is 0.55%; solid content is 99.45%; number average molecular weight is 1128; molecular weight distribution is 1.16; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0096] Reaction Example 6

[0097] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.050g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.88%.

[0098] 2. After water removal, the purity of the obtained natural phytosterols is 99.12%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure during EO addition is controlled to not exceed 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0099] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0100] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0101] After testing: moisture content is 0.56%; solid content is 99.44%; number average molecular weight is 1150; molecular weight distribution is 1.16; surface tension at 25℃ is 33 mN / m; HLB value is 10.

[0102] Reaction Example 7

[0103] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.5g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.88%.

[0104] 2. After water removal, the purity of the obtained natural phytosterols is 99.12%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (35 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (29 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0105] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0106] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0107] After testing: moisture content is 0.58%; solid content is 99.42%; number average molecular weight is 1140; molecular weight distribution is 1.15; surface tension at 25℃ is 32 mN / m; HLB value is 10.

[0108] Reaction Example 8

[0109] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.5g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.88%.

[0110] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0111] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0112] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0113] After testing: moisture content is 0.61%; solid content is 99.39%; number average molecular weight is 1130; molecular weight distribution is 1.18; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0114] Reaction Example 9

[0115] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.5g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.88%.

[0116] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0117] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0118] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0119] After testing: moisture content is 0.59%; solid content is 99.41%; number average molecular weight is 1135; molecular weight distribution is 1.17; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0120] Reaction Example 10

[0121] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.5g of composite catalyst (including 0.4g of potassium hydroxide solution (50%) and 0.1g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.88%.

[0122] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0123] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0124] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0125] After testing: moisture content is 0.59%; solid content is 99.41%; number average molecular weight is 1135; molecular weight distribution is 1.17; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0126] Reaction Example 11

[0127] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.76%.

[0128] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0129] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0130] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0131] After testing: moisture content is 0.12%; solid content is 99.88%; number average molecular weight is 1128; molecular weight distribution is 1.17; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0132] Reaction Example 12

[0133] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.76%.

[0134] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (35 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (29 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0135] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1.5 hours.

[0136] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0137] After testing: moisture content is 0.25%; solid content is 99.75%; number average molecular weight is 1140; molecular weight distribution is 1.11; surface tension at 25℃ is 32mN / m; HLB value is 10.

[0138] Reaction Example 13

[0139] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.76%.

[0140] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0141] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0142] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0143] After testing: moisture content is 0.38%; solid content is 99.62%; number average molecular weight is 1120; molecular weight distribution is 1.18; surface tension at 25℃ is 35 mN / m; HLB value is 12.

[0144] Reaction Example 14

[0145] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.76%.

[0146] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0147] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0148] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0149] After testing: moisture content is 0.27%; solid content is 99.73%; number average molecular weight is 1142; molecular weight distribution is 1.15; surface tension at 25℃ is 32 mN / m; HLB value is 10.

[0150] Reaction Example 15

[0151] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of composite catalyst (including 0.23g of potassium hydroxide solution (50%) and 0.035g of triethanolamine) to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.76%.

[0152] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0153] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0154] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0155] After testing: moisture content is 0.26%; solid content is 99.74%; number average molecular weight is 1141; molecular weight distribution is 1.15; surface tension at 25℃ is 32 mN / m; HLB value is 10.

[0156] Reaction Example 16

[0157] 1. Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydrate under vacuum (-0.098MPa) for 1.5 hours, and the moisture content is measured to be 0.91%.

[0158] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0159] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0160] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0161] After testing: moisture content is 0.62%; solid content is 99.38%; number average molecular weight is 1150; molecular weight distribution is 1.15; surface tension at 25℃ is 32 mN / m; HLB value is 10.

[0162] Reaction Example 17

[0163] 1. Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydrate under vacuum (-0.098MPa) for 1.5 hours, and the moisture content is measured to be 0.91%.

[0164] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (35 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (29 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0165] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0166] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0167] After testing: moisture content is 0.79%; solid content is 99.21%; number average molecular weight is 1130; molecular weight distribution is 1.17; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0168] Reaction Example 18

[0169] 1. Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydrate under vacuum (-0.098MPa) for 1.5 hours, and the moisture content is measured to be 0.91%.

[0170] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0171] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0172] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0173] After testing: moisture content is 0.83%; solid content is 99.17%; number average molecular weight is 1121; molecular weight distribution is 1.18; surface tension at 25℃ is 35 mN / m; HLB value is 12.

[0174] Reaction Example 19

[0175] 1. Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydrate under vacuum (-0.098MPa) for 1.5 hours, and the moisture content is measured to be 0.91%.

[0176] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.5 mol / h (22 g / h). The reaction pressure is controlled to not exceed 0.4 MPa during the addition of EO. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (46 g / h), with the reaction pressure strictly controlled to not exceed 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0177] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0178] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0179] After testing: moisture content is 0.8%; solid content is 99.2%; number average molecular weight is 1128; molecular weight distribution is 1.17; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0180] Reaction Example 20

[0181] 1. Add 100g of a mixture of β-sitosterol and stigmasterol with a purity ≥95% to a 1000ML high-pressure reactor, along with 0.531g of a composite catalyst (containing 0.462g of potassium hydroxide solution (50%) and 0.069g of triethanolamine). After purging with nitrogen three times, turn on the vacuum device to perform a vacuuming operation. Simultaneously, start heating to 130℃ for moisture removal. Dehydrate under vacuum (-0.098MPa) for 1.5 hours, and the moisture content is measured to be 0.91%.

[0182] 2. After water removal, the purity of the obtained natural phytosterols is 99.26%. The temperature is initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 1 mol / h (44 g / h). The reaction pressure during EO addition is controlled to be no greater than 0.4 MPa. After all EO has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor drops to a constant 0.25 MPa. Then, 69.70 g of propylene oxide (PO) is slowly added dropwise to the reactor at a rate of 0.3 mol / h (17 g / h), with the reaction pressure strictly controlled to be no greater than 0.5 MPa. After the addition is complete, the reaction is maintained at this temperature for another 3 hours, until the pressure inside the reactor drops to a constant 0.3 MPa.

[0183] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1 hour.

[0184] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0185] After testing: moisture content is 0.81%; solid content is 99.19%; number average molecular weight is 1125; molecular weight distribution is 1.17; surface tension at 25℃ is 34 mN / m; HLB value is 11.

[0186] As can be seen from reaction examples 1-20, the detection index of reaction example 12 is the best, so it is compared with it.

[0187] Comparative Example 1

[0188] Compared with Reaction Example 12, the only difference is that the composite catalyst in Reaction Example 12 is replaced with 0.265g of potassium hydroxide solution.

[0189] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of potassium hydroxide solution (50%) as catalyst to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.96%.

[0190] 2. After removing moisture, the purity of the obtained natural plant sterols is 99.04%. The temperature is initially raised to 150℃. Under a nitrogen atmosphere, the initial pressure inside the reactor is 0.15 MPa. 105.72 g of ethylene oxide (EO) is slowly added dropwise to the reactor at a rate of 0.8 mol / h (35 g / h). At this point, the reaction pressure rises rapidly. The rate of ethylene oxide (EO) addition is reduced to control the reaction pressure to not exceed 0.4 MPa. After all the ethylene oxide (EO) has been added, the reaction is maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully until the pressure inside the reactor drops to a constant 0.25 MPa. Then, continue to slowly add 69.70 g of propylene oxide (PO) dropwise into the reactor at a rate of 0.5 mol / h (29 g / h). Strictly control the reaction pressure to not exceed 0.5 MPa (the potassium hydroxide catalyst reacts violently during the initial EO addition). After the addition is complete, continue to maintain the temperature for 3 hours until the pressure inside the reactor drops to a constant 0.3 MPa. (Because the potassium hydroxide catalyst is strongly alkaline, its use alone can accelerate the reaction rate. However, changes in the rate of EO addition can affect the distribution of product blocks, impacting the final product conversion rate and leading to unreacted phytosterols and small molecule oligomers remaining in the product. Furthermore, explosive polymerization can occur during the polymerization process. Therefore, using potassium hydroxide catalyst alone is not recommended.)

[0191] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1.5 hours.

[0192] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0193] After testing: moisture content is 0.68%; solid content is 99.32%; number average molecular weight is 968; molecular weight distribution is 1.62; surface tension at 25℃ is 40mN / m; HLB value is 8.

[0194] Comparative Example 2

[0195] Compared with Reaction Example 12, the only difference is that the composite catalyst in Reaction Example 12 is replaced with 0.265g of triethanolamine.

[0196] 1. Add 100g of β-sitosterol with a purity ≥95% and 0.265g of triethanolamine catalyst to a 1000ML high-pressure reactor. After purging with nitrogen three times, turn on the vacuum device to perform vacuuming. At the same time, start heating to 130℃ to remove moisture. Dehydrate under vacuum (-0.098MPa) for 1.5h and measure the moisture content to be 0.43%.

[0197] 2. After water removal, the purity of the obtained natural phytosterols was 99.57%. The temperature was initially raised to 150℃ under a nitrogen atmosphere, with an initial pressure of 0.15 MPa inside the reactor. 105.72 g of ethylene oxide (EO) was slowly added dropwise to the reactor at a rate of 0.8 mol / h (35 g / h). During the addition, the reaction pressure remained essentially constant. After sixteen hours, the reaction pressure began to rise, reaching a maximum of 0.3 MPa. The reaction was maintained at this temperature for 2 hours to allow the ethoxylation reaction to proceed fully, until the pressure inside the reactor dropped to a constant 0.25 MPa. At this point, 69.70 g of propylene oxide (PO) was slowly added dropwise to the reactor at a rate of 0.5 mol / h (29 g / h). The maximum reaction pressure reached 0.28 MPa. After the addition was complete, the reaction was maintained at this temperature for another 3 hours, until the pressure inside the reactor dropped to a constant 0.26 MPa. (Because the catalyst triethanolamine has low activity and a slow reaction rate, using it alone will result in an incomplete reaction and failure to obtain the final desired product. Therefore, it is not recommended to use triethanolamine catalyst alone.)

[0198] 3. After the reaction is complete, cool the system to 60°C, add 0.3g of glacial acetic acid for neutralization, and measure the pH to be 5.5-8.0. Continue to turn on the vacuum device, with a vacuum pressure of -0.096 MPa, and heat to 140°C to remove low-boiling substances under vacuum for 1.5 hours.

[0199] 4. After removing low-boiling substances, cool to 70°C and discharge the material to obtain narrow-distribution phytosterol EO / PO block polyether.

[0200] Testing revealed the following: due to poor water solubility, the moisture content, number-average molecular weight, molecular weight distribution, and surface tension at 25°C could not be measured; the solid content was 98.46%.

[0201] As shown in Comparative Examples 1-2, neither potassium hydroxide solution alone nor triethanolamine as a catalyst is as effective as the synergistic effect of the composite catalyst.

[0202] The rates of addition of ethylene oxide (EO) and propylene oxide (PO) in this method require strict control. The dropping rate of EO is 0.5-1.0 mol / h, with the reaction pressure controlled at ≤0.4 MPa and the reaction time maintained at this temperature for 3 hours. The dropping rate of propylene oxide (PO) is 0.3-0.8 mol / h, with the reaction pressure controlled at ≤0.5 MPa and the reaction time maintained at this temperature for 4 hours. However, the amounts of EO and PO added can be varied. Different amounts will yield narrow-distribution phytosterol EO / PO block polyether products with varying properties. Only by controlling the dropping rates of EO and propylene oxide under the action of a composite catalyst can the uniformity of EO / PO chain length during the reaction be effectively controlled.

[0203] Comprehensive analysis

[0204] As can be seen from the pretreatment examples 1-8,

[0205] 1. The less mixed catalyst is added to natural phytosterols, the less water content and the higher the purity of natural phytosterols under the same removal time.

[0206] 2. When equal amounts of mixed catalyst are added to natural phytosterols, the longer the removal time, the lower the water content of the natural phytosterols and the higher their purity.

[0207] As can be seen from reaction examples 1-20,

[0208] 1. The addition of composite catalysts not only improves the reaction rate and selectivity, but also changes the chemical properties of the reaction. As the auxiliary catalyst helps the main catalyst potassium hydroxide to regulate the alkalinity and acidity of the reaction, inhibits the chain transfer reaction, and narrows the molecular weight distribution, the two catalysts work synergistically to promote the complete ethoxylation and propoxylation reactions and promote the formation of the target product.

[0209] 2. The rate of addition of ethylene oxide (EO) and propylene oxide (PO) in this method requires strict and precise control. However, the amount of EO and PO added can be varied. Depending on the amount added, narrow-distribution phytosterol EO / PO block polyether products with different properties can be obtained. Only by controlling the rate of addition of ethylene oxide and propylene oxide under the action of a composite catalyst can the uniformity of EO / PO chain length during the reaction be effectively controlled, the molecular weight distribution narrowed, and the water solubility of phytosterols effectively improved.

[0210] 3. The indicators of the narrow-distribution phytosterol EO / PO block polyether obtained after testing are within the following range.

[0211] Moisture content ≤1%, purity ≥99%, molecular weight distribution ≤1.2; HLB value 9-14; surface tension at 25℃ is 31-38mN / m.

[0212] The applicant declares that this invention illustrates the phytosterol EO / PO block polyether, its preparation method, and its application through the above embodiments. However, this invention is not limited to the above embodiments, meaning that this invention does not necessarily rely on the above embodiments for implementation. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of raw materials for the product, addition of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. A phytosterol EO / PO block polyether, characterized in that, The phytosterol EO / PO block polyether has the following structure: ； Where R represents a phytosterol residue, m is 1-10, and n is 2-30.

2. The phytosterol EO / PO block polyether according to claim 1, characterized in that, R is selected from the following groups: , or .

3. The method for preparing phytosterol EO / PO block polyether according to claim 1 or 2, characterized in that, The preparation method includes the following steps: Under the catalysis of a composite catalyst, natural phytosterols react with ethylene oxide, and then with propylene oxide to obtain the phytosterol EO / PO block polyether; the composite catalyst includes potassium hydroxide as the main catalyst and triethanolamine as the auxiliary catalyst.

4. The preparation method according to claim 3, characterized in that, The mass ratio of potassium hydroxide to triethanolamine is 1:0.3-0.

5.

5. The preparation method according to claim 3, characterized in that, The amount of the composite catalyst added is 0.15%-0.3% of the mass of natural phytosterols.

6. The preparation method according to any one of claims 3-5, characterized in that, The phytosterol is one of stigmasterol or β-sitosterol, or a mixture thereof.

7. The preparation method according to any one of claims 3-6, characterized in that, Before the reaction, the natural plant sterols and the composite catalyst are dehydrated. Preferably, the dehydration process involves vacuum dehydration under a nitrogen atmosphere, with the dehydration temperature at 130°C and the dehydration time at 1-2 hours, until the moisture content is ≤1%. Preferably, the molar ratio of the natural phytosterols to ethylene oxide is 1:2-30; Preferably, the reaction temperature of the natural phytosterols with ethylene oxide is 150-160°C, and the reaction time is 2-4 hours; Preferably, the ethylene oxide is added to the reaction system dropwise; Preferably, the dropping rate of the ethylene oxide is 0.5-1.0 mol / h; Preferably, the reaction of the natural phytosterols with ethylene oxide is carried out under nitrogen protection. Preferably, the reaction of the natural phytosterols with ethylene oxide is carried out at a pressure of ≤0.4 MPa.

8. The preparation method according to any one of claims 3-7, characterized in that, The molar ratio of the natural phytosterols to propylene oxide is 1:1-10; Preferably, the propylene oxide is added to the reaction system dropwise; Preferably, the dropping rate of the propylene oxide is 0.3-0.8 mol / h; Preferably, the reaction temperature with propylene oxide is 150℃-160℃, and the reaction time is 3-5 hours; Preferably, the reaction with propylene oxide is carried out under nitrogen protection; Preferably, the reaction with propylene oxide is carried out at a pressure of ≤0.5 MPa.

9. The preparation method according to any one of claims 3-8, characterized in that, After the reaction with propylene oxide is completed, the temperature is lowered to 60-70℃, glacial acetic acid is added for neutralization, the pH is 5.5-8, and then low-boiling substances are removed under vacuum. Preferably, the temperature for vacuum removal of low-boiling substances is 90°C, the vacuum degree is ≤-0.098MPa, and the removal time is 1-1.5h; Preferably, the temperature is lowered to 70-80°C after removing low-boiling substances.

10. The phytosterol EO / PO block polyether according to claim 1 or 2 can be used in cosmetics, food and pharmaceuticals.

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