Alkyl glucoside derivative and preparation method thereof

Abstract

The invention belongs to the technical field of daily chemicals, and particularly relates to an alkyl glucoside derivative and a preparation method thereof. The alkyl glucoside derivative provided by the invention is prepared by carrying out chemical modification on hydroxyl activity on a glucoside unit, specifically, carrying out cross-linking through a cross-linking agent, and then introducing an anionic sulfonic acid group. The molecular weight of the alkyl glucoside derivative subjected to sulfonation modification is obviously increased, the transdermal permeability can be reduced, the residual quantity of a surfactant on the skin is reduced, meanwhile, larger micelles can be formed, the irritation of the surfactant to the skin is reduced, and the alkyl glucoside derivative has relatively high mildness and can be used for preparing the skin care product. The method is suitable for preparing products with high requirements on tenderness. In addition, the preparation method of the alkyl glucoside derivative provided by the invention also has the advantages of high yield (93% or above), simple operation and high repeatability, and is beneficial to popularization and application of the preparation process of the alkyl glucoside derivative.

Description

Technical Field

[0001] This invention belongs to the field of daily chemical products technology, specifically relating to an alkyl glucoside derivative and its preparation method. Background Technology

[0002] Alkyl glucosides (APGs) are a class of nonionic surfactants formed by the condensation reaction of glycosyl groups (glucose) and fatty alcohols. With increasing environmental awareness, the pollution problems of traditional synthetic surfactants are becoming increasingly prominent. Due to their natural source, biodegradability, and low toxicity, APGs are rapidly being promoted in the fields of detergents, cosmetics, and food. APGs have many advantages in application: (1) Environmental friendliness: APGs can be rapidly degraded in the environment, reducing pollution and meeting the needs of sustainable development. (2) Mildness: APGs have low skin irritation and are suitable for personal care products (such as shampoos and skin care products). (3) Multifunctionality: APGs have emulsifying, dispersing, and antibacterial properties and are widely used in detergents, food additives (such as dairy stabilizers), agricultural biological pesticides, and pharmaceuticals (such as antiviral adjuvants). (4) Stability: APGs have high stability over a wide range of pH and temperature.

[0003] Despite its significant advantages, APG also has certain drawbacks depending on the application scenario and requirements. These include relatively high cost, complex synthesis processes, insufficient stability of some APGs under extreme conditions such as high salt and high temperature, and a narrow antibacterial spectrum, requiring combination with other ingredients to enhance efficacy. Taking the application of APG in personal care products as an example, its shortcomings mainly lie in: its relatively strong permeability due to its non-ionic structure, strong deproteinizing / degreasing ability, and large adsorption capacity in the stratum corneum, which can lead to some damage to the skin barrier, a slippery feeling after washing, and a significant dryness after drying, especially in autumn and winter.

[0004] To improve the performance of APG, altering the alkyl chain length, sugar group type, or introducing functional groups can all improve APG derivatives to varying degrees, mitigating its defects. These derivatives can be applied in different scenarios, greatly enhancing the application value of APG. Currently, the synthesis methods for APG derivatives still face many challenges, mainly manifested in low conversion rates, poor regioselectivity of the synthesis reactions, and difficulties in separating the resulting mixtures or high separation costs. These issues severely restrict the large-scale industrial production of APG derivatives. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an alkyl glucoside derivative with high yield, low production cost, and excellent surface chemical properties, as well as a method for its preparation. The alkyl glucoside derivative provided by this invention involves chemically modifying the hydroxyl activity on the glucoside sugar unit. The sulfonated alkyl glucoside derivative exhibits a significantly increased molecular weight, which not only reduces transdermal penetration and surfactant residue on the skin but also facilitates the formation of larger micelles, reducing surfactant irritation to the skin and exhibiting higher mildness.

[0006] The technical solution of the present invention is as follows: This invention provides an alkyl glucoside derivative, which is shown in Formula I: Formula I; Among them, the R1 group is or The R2 group is Or H; or the same as the R1 group; x = 1~4; y = 1~10, which represents the degree of aggregation of EO; z = 1~3, which represents the degree of polymerization of APG molecules; R is C8-C 20 The alkyl group, preferably C8-C 10 Alkyl, C8-C 14 Alkyl, C8-C 16 Alkyl, C8-C 18 Alkyl, C 10 -C 12 Alkyl, C 10 -C 14 Alkyl, C 10 -C 16 Alkyl, C 10 -C 18 Alkyl, C 12 -C 14 Alkyl, C 12 -C 16 Alkyl, C 12 -C 18 Alkyl, C 12 -C 20 Alkyl, octyl (C8), decyl (C8) 10 ), Laureth (C 12 ), myristyl (C 14 ).

[0007] Furthermore, in the alkyl glucoside derivative, when x=1, R2 is H; R1 is... Where z = 1~3, and R is C8-C 20The alkyl group, the C8-C 20 The alkyl group is preferably C8-C 10 Alkyl, C8-C 14 Alkyl, C8-C 16 Alkyl, C8-C 18 Alkyl, C 10 -C 12 Alkyl, C 10 -C 14 Alkyl, C 10 -C 16 Alkyl, C 10 -C 18 Alkyl, C 12 -C 14 Alkyl, C 12 -C 16 Alkyl, C 12 -C 18 Alkyl, C 12 -C 20 Alkyl, octyl (C8), decyl (C8) 10 ), Laureth (C 12 ), myristyl (C 14 ).

[0008] Furthermore, in the alkyl glucoside derivatives, when x = 2~4, R1 = R2, specifically as follows: Where y = 1~10, z = 1~3, and R is C8-C 20 The alkyl group, the C8-C 20 The alkyl group is preferably C8-C 10 Alkyl, C8-C 14 Alkyl, C8-C 16 Alkyl, C8-C 18 Alkyl, C 10 -C 12 Alkyl, C 10 -C 14 Alkyl, C 10 -C 16 Alkyl, C 10 -C 18 Alkyl, C 12 -C 14 Alkyl, C 12 -C 16 Alkyl, C 12 -C 18 Alkyl, C 12 -C 20 Alkyl, octyl (C8), decyl (C8) 10 ), Laureth (C 12 ), myristyl (C 14 ).

[0009] In addition, the present invention also provides a method for preparing an alkyl glucoside derivative, comprising the following steps: Step S1: Add the alkyl glucoside solution and solvent to the reaction vessel, heat to 75-85 °C at 200-400 rpm, and stir for 30-60 min; Step S2: Add the activator to the reaction vessel from step S1 and react. Heat the mixture to 85-90 °C at a rate of 400-600 rpm and react for 1-2 h. Step S3: Add the crosslinking agent to the reaction vessel in step S2 to carry out the reaction, monitor the conversion rate, and stop the reaction after the requirement is reached; Step S4: Add the sulfonating agent to the reaction vessel in step S3 and react. Monitor the conversion rate and stop the reaction when the required conversion rate is reached. Cool to 15~20 ℃, let stand for 12~24 h, filter, take the filtrate, dry under reduced pressure, and remove the solvent to obtain the final product.

[0010] Furthermore, the alkyl glucoside in step S1 is C 12 -C 16 Alkyl glucoside, C 12 -C 18 Alkyl glucoside, C 12 -C 20 Alkyl glucoside, C8-C 14 One or more of alkyl glucoside, octyl glucoside, decyl glucoside, octyl / decyl glucoside, lauryl glucoside, myristyl glucoside, and cocoyl glucoside; wherein the mass ratio of the alkyl glucoside solution to the solvent is (1.5~5):1.

[0011] Furthermore, the alkyl glucoside is obtained by reacting a straight-chain fatty alcohol with glucose, wherein the free fatty alcohol content is <1.0% and the free glucose content is <0.5%; the alkyl glucoside solution of the present invention is an alkyl glucoside with an active ingredient content of 50%.

[0012] Further, the solvent in step S1 is at least one of water, methanol, ethanol, isopropanol, acetone, and tetrahydrofuran; or at least one of a mixture of water and methanol, water and ethanol, water and isopropanol, water and acetone, and water and tetrahydrofuran; if a mixture of water and an organic solvent is selected, the volume ratio is (1~2):1.

[0013] Furthermore, the activator is one of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium carbonate, potassium carbonate, and solid superbase catalyst, and the mass ratio of the activator to the alkyl glucoside solution is 1:(15~30).

[0014] Furthermore, the solid superbase catalyst can be obtained commercially, such as HND-61, HND-62, HND-63, and HND-64, which are obtained by supporting potassium carbonate on activated alumina and then sintering.

[0015] In this invention, if a water-soluble activator is selected, subsequent treatment can be omitted, and the next reaction can proceed directly. If a solid superbase catalyst is selected, solid-liquid separation should be performed after the reaction, and the liquid should be collected for the next reaction. The separation includes, but is not limited to, centrifugation, filtration, vacuum filtration, and pressure filtration; preferably, filtration is done through a 200-mesh filter.

[0016] Further, in step S3, the crosslinking agent is multi-arm polyethylene glycol chloride or 1,3-dichloro-2-propanol, and the molar ratio of the crosslinking agent to the alkyl glucoside is (0.2~0.3):1. The temperature is increased to 90~95 °C at a speed of 100~200 rpm, and the reaction is carried out for 6~8 h.

[0017] Furthermore, the conversion rate of the crosslinking agent was monitored by HPLC, and the residual amount was ≤0.1 ppm (detection concentration 0.005 ppm, minimum quantitative concentration 0.025 ppm).

[0018] Furthermore, the structure of the multi-arm polyethylene glycol chloride is as follows: Where m=2~6; n=1~3; molecular weight 0.4~2 K; for example: 6-ArmPEG-Cl (four-armed polyethylene glycol-chloride), 8-ArmPEG-Cl (six-armed polyethylene glycol-chloride), etc.

[0019] Further, the sulfonating agent in step S4 is one of sodium 2-chloroethylsulfonate, sodium 3-chloro-2-hydroxypropanesulfonate, and sodium 4-chloro-1-hydroxybutanesulfonate. The molar ratio of the sulfonating agent to the alkyl glucoside is (1.2~2.0):1. The temperature is increased to 80~85 °C at a speed of 200~400 rpm, and the reaction is carried out for 3~5 h.

[0020] Furthermore, the conversion rate of the sulfonating agent is monitored by HPLC, and the residual amount is ≤0.1% (detection concentration 0.1%, minimum quantitative concentration 0.1%).

[0021] Furthermore, the filtration in step S4 is mainly used to separate the particulate matter precipitated during the settling process, preferably using a 200-mesh filter; the reduced pressure drying can be carried out by methods including but not limited to vacuum drying and freeze drying, the purpose of which is to remove the contained solvent.

[0022] The alkyl glucoside derivatives obtained by this invention have a solid content ≥96%. HPLC analysis shows that the alkyl polysaccharide sulfonate derivative content is ≥86%, nonionic matter ≤10%, inorganic salts ≤4.0%, and the residual crosslinking agent and sulfonating agent are both below the detection limit. The obtained alkyl glucoside derivatives can also be diluted with water to achieve solid contents of 60%, 50%, and 40% to suit different applications.

[0023] The alkyl glucoside derivatives provided by this invention are prepared by chemically modifying the hydroxyl groups on the glucoside sugar units. Specifically, they are first cross-linked with a cross-linking agent and then anionic sulfonic acid groups are introduced. The sulfonated alkyl glucoside derivatives of this invention have a significantly larger molecular weight, which not only reduces transdermal penetration and the amount of surfactant residue on the skin, but also helps to form larger micelles, reducing the irritation of surfactants to the skin. They exhibit high mildness and are suitable for formulating products with high mildness requirements, such as baby products and facial cleansers.

[0024] Meanwhile, the preparation method of alkyl glucoside derivatives provided by the present invention also has the advantages of high yield (over 93%), simple operation, and high reproducibility, which is conducive to the promotion and application of the preparation process of alkyl glucoside derivatives.

[0025] In summary, compared with the prior art, the alkyl glucoside derivatives provided by the present invention have the following advantages: (1) The alkyl glucoside derivatives provided by the present invention have the advantages of high mildness, low irritation, low residue and easy washing. They can effectively solve the defects of alkyl glucosides in personal cleaning products, such as strong deproteinization / degreasing ability, high irritation and large residue. They can effectively expand the application of alkyl glucosides.

[0026] (2) The preparation process of the alkyl glucoside derivative provided by the present invention has the advantages of high yield (over 93%), simple operation, and high repeatability, which is conducive to the large-scale promotion and application of the production process. Detailed Implementation

[0027] The present invention will be further described below through specific embodiments, but this is not intended to limit the invention. Those skilled in the art can make various modifications or improvements based on the basic idea of ​​the invention, but as long as they do not depart from the basic idea of ​​the invention, they are all within the scope of the invention. The materials and reagents involved in the present invention can all be obtained commercially available or through conventional techniques in the art.

[0028] Example 1, C 12 -C 16 Preparation of alkyl glucoside derivatives Step S1: Take 696 g of C12 -C 16 Alkyl glucoside solution (1.0 mol, at C 12 -C 16 alkyl glucoside, molecular formula: Mn=348 g / mol), the C 12 -C 16 Alkyl glucoside solution is C 12 -C 16 A mixture of alkyl glucoside and water, C 12 -C 16 The mass ratio of alkyl glucoside to water is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%. 232 g of water / methanol (V:V=1:1) mixed solvent (the mass ratio of water / methanol mixed solvent to C12-C16 alkyl glucoside solution is 1:3) is added to the reaction vessel, and the temperature is raised to 75 °C at 200 rpm and stirred for 30 min until the mixture is homogeneous. Step S2: Mix 34.8 g of sodium hydroxide (sodium hydroxide with C) 12 -C 16 The alkyl glucoside solution (mass ratio 1:20) was added to the reaction vessel in step S1 and reacted. The temperature was raised to 85 °C at 400 rpm and reacted for 1 h. Step S3: Add 100 g of four-arm polyethylene glycol chloride (4-ArmPEG-Cl, 0.25 mol, Mn=400 g / mol) to the reaction vessel in step S2, heat to 90 °C at 100 rpm and react for 6 h, monitor the crosslinking agent conversion rate until the residual amount is 0.1 ppm, and stop the reaction after the requirement is met; Step S4: Add 252.9 g of sodium 2-chloroethylsulfonate (1.5 mol, molecular formula: Add Mn=168.6 g / mol to the reaction vessel in step S3, heat to 80 °C at 200 rpm and react for 3 h. Monitor the conversion rate of the sulfonating agent until no residual amount is detected. Stop the reaction after reaching the required level, cool to 15 °C, let stand for 12 h, filter through a 200-mesh filter, and take C. 12 -C 16 An alkyl glucoside derivative solution was dried under vacuum to obtain C. 12 -C 16 Alkyl glucoside derivative (721.5g).

[0029] Testing revealed a solid content of 96%, and HPLC analysis showed that C 12 -C 16The content of alkyl glucoside derivatives was 86%, nonionic substances were 10%, inorganic salts were 4.0%, and the residual amount of crosslinking agent and sulfonating agent was not detected. The calculated reaction yield of this example was 93.41%.

[0030] Example 2: Preparation of lauryl glucoside derivatives Step S1: Take 696 g of lauryl glucoside solution (1.0 mol, calculated as lauryl glucoside, molecular formula: The lauryl glucoside solution (Mn=348 g / mol) is a mixture of lauryl glucoside and water, with a mass ratio of lauryl glucoside to water of 50:50, a free fatty alcohol content of <1.0%, and a free glucose content of <0.5%. 261 g of a water / ethanol (V:V=2:1) ​​mixed solvent (the mass ratio of the water / methanol mixed solvent to the lauryl glucoside solution is 1:2.67) is added to the reaction vessel, and the temperature is raised to 80 °C at 300 rpm and stirred for 45 min until the mixture is homogeneous. Step S2: Add 34.8 g of sodium carbonate (sodium carbonate to lauryl glucoside solution in a mass ratio of 1:20) to the reaction vessel in step S1 and react at 90 °C for 1.5 h at 500 rpm. Step S3: Add 167 g of six-arm polyethylene glycol chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) to the reaction vessel in step S2, heat to 92 °C at 150 rpm and react for 7 h, monitor the crosslinking agent conversion rate until no residual amount is detected, and stop the reaction after the requirement is met; Step S4: Add 297.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, molecular formula: Add Mn=196.59 g / mol to the reaction vessel in step S3, heat to 82 °C at 300 rpm and react for 4 h. Monitor the conversion rate of the sulfonating agent until no residual amount is detected. Stop the reaction after reaching the required level, cool to 16 °C, let stand for 15 h, filter through a 200-mesh filter, take the lauryl glucoside derivative solution, and vacuum dry to obtain lauryl glucoside derivative (825.7 g).

[0031] The solid content was found to be 98%. HPLC analysis showed that the lauryl glucoside derivative content was 90%, nonionic matter was 8%, inorganic salts were 3.5%, and no residual crosslinking agent or sulfonating agent was detected. The reaction yield of this example was calculated to be 98.84%.

[0032] Example 3, C8-C 14 Preparation of alkyl glucoside derivatives Step S1: Take 640 g of C8-C 14 Alkyl glucoside solution (1.0 mol, in C8-C) 14 alkyl glucoside, molecular formula: C 16 H 32 O6, Mn=320 g / mol), the C8-C 14 Alkyl glucoside solution is C8-C 14 A mixture of alkyl glucoside and water, C8-C 14 The alkyl glucoside and water mass ratio is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%; 256 g of water / isopropanol (V:V=1.5:1) mixed solvent (water / methanol mixed solvent and C8-C 14 The alkyl glucoside solution (mass ratio 1:2.5) was added to the reaction vessel, heated to 85 °C at 250 rpm, and stirred for 60 min until homogeneous. Step S2: Mix 32 g of solid superalkali HND-61 (HND-61 and C8-C 14 The alkyl glucoside solution (mass ratio 1:20) was added to the reaction vessel in step S1 and reacted. The temperature was raised to 86 °C at 600 rpm and reacted for 2 h. After the reaction was completed, the mixture was filtered through a 200-mesh filter to remove solid particles. Step S3: Add 167 g of six-arm polyethylene glycol chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) to the reaction vessel in step S2, heat to 95 °C at 200 rpm and react for 8 h, monitor the crosslinking agent conversion rate until no residual amount is detected, and stop the reaction after the requirement is met; Step S4: Add 315.9 g of sodium 4-chloro-1-hydroxy-butanesulfonate (1.5 mol, Mn=210.61 g / mol) to the reaction vessel from step S3. Heat to 85 °C at 250 rpm and react for 5 h. Monitor the sulfonating agent conversion rate until the residual amount reaches 0.1%. Stop the reaction after reaching the required level, cool to 20 °C, and let stand for 20 h. Filter through a 200-mesh screen and collect C8-C. 14 Alkyl glucoside derivative solution, freeze-dried, to give C8-C 14 Alkyl glucoside derivative (784.6 g).

[0033] Testing revealed a solid content of 97%, and HPLC analysis showed that it contained C8-C. 14 The content of alkyl glucoside derivatives was 88%, nonionic matter was 9%, inorganic salts were 3.7%, and the residual amount of crosslinking agent and sulfonating agent was not detected. The reaction yield of this embodiment was calculated to be 95.02%.

[0034] Example 4: Preparation of octyl / decyl glucoside derivatives Step S1: Dissolve 814 g of octyl / decyl glucoside solution (1.0 mol, calculated as octyl / decyl glucoside, molecular formula: C...). 22 H 46 O6, Mn=407 g / mol), the octyl / decyl glucoside solution is a mixture of octyl / decyl glucoside and water, the mass ratio of octyl / decyl glucoside to water is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%; 271.3 g of isopropanol (the mass ratio of isopropanol to octyl / decyl glucoside solution is 1:3) is added to the reaction vessel, the temperature is raised to 75 °C at 400 rpm, and the mixture is stirred for 35 min until it is homogeneous; Step S2: Add 32.56 g of sodium methoxide (sodium methoxide to octyl / decyl glucoside solution in a mass ratio of 1:25) to the reaction vessel in step S1 and react at 88 °C for 1.5 h at 450 rpm. Step S3: Add 250 g of octagonal-polyethylene glycol chloride (8-ArmPEG-Cl, 0.125 mol, Mn=2000 g / mol) to the reaction vessel in step S2, heat to 91 °C at 120 rpm and react for 6.5 h. Monitor the crosslinking agent conversion rate until no residual amount is detected, and stop the reaction after the requirement is met. Step S4: Add 297.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, molecular formula: C3H6ClNaO4S, Mn=196.59 g / mol) to the reaction vessel in step S3, heat to 81 °C at 400 rpm and react for 3.5 h. Monitor the conversion rate of the sulfonating agent until the residual amount is 0.01 ppm. Stop the reaction after reaching the requirement, cool to 18 °C, let stand for 24 h, filter through a 200-mesh filter, take the octyl / decyl glucoside derivative solution, freeze dry to obtain octyl / decyl glucoside derivative (906.8 g).

[0035] The solid content was found to be 96.5%. HPLC analysis showed that the content of octyl / decyl glucoside derivative was 87%, nonionic matter was 7%, inorganic salts were 3.8%, and no residual crosslinking agent or sulfonating agent was detected. The reaction yield of this example was calculated to be 96.78%.

[0036] Example 5: Preparation of coconut oil-based glucoside derivatives Step S1: Take 696 g of coco-glucoside solution (1.0 mol, calculated as coco-glucoside, English name: COCO-GLUCOSIDE, molecular formula: ...). The cocoyl glucoside solution (Mn=348 g / mol) is a mixture of cocoyl glucoside and water, with a mass ratio of cocoyl glucoside to water of 50:50, a free fatty alcohol content of <1.0%, and a free glucose content of <0.5%. 348 g of water (with a mass ratio of water to cocoyl glucoside solution of 1:2) is added to the reaction vessel, and the temperature is raised to 80 °C at 350 rpm and stirred for 45 min until the mixture is homogeneous. Step S2: Add 39.77 g of sodium hydroxide (the mass ratio of sodium hydroxide to cocoyl glucoside solution is 1:17.5) to the reaction vessel in step S1 and react at 85 °C for 1.2 h at 550 rpm. Step S3: Add 167 g of six-arm polyethylene glycol chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) to the reaction vessel in step S2, heat to 94 °C at 160 rpm and react for 7 h, monitor the crosslinking agent conversion rate until the residual amount is 0.05 ppm, and stop the reaction after the requirement is met; Step S4: Add 315.9 g of sodium 4-chloro-1-hydroxy-butanesulfonate (1.5 mol, Mn=210.61 g / mol) to the reaction vessel in step S3, heat to 84 ℃ at 350 rpm and react for 4 h. Monitor the conversion rate of the sulfonating agent until no residual amount is detected. Stop the reaction after reaching the required level, cool to 19 ℃, let stand for 18 h, filter through a 200-mesh filter, take the coco-glucoside derivative solution, and vacuum dry to obtain coco-glucoside derivative (781.5 g).

[0037] The solid content was 97%, and HPLC analysis showed that the content of cocoa-glucoside derivative was 88%, nonionic matter was 8.5%, inorganic salts were 3.6%, and no residual crosslinking agent or sulfonating agent was detected. The reaction yield of this example was calculated to be 97.63%.

[0038] Example 6: Preparation of lauryl glucoside derivatives Step S1: Take 696 g of lauryl glucoside solution (1.0 mol, calculated as lauryl glucoside, molecular formula: The lauryl glucoside solution (Mn=348 g / mol) is a mixture of lauryl glucoside and water, with a mass ratio of lauryl glucoside to water of 50:50, a free fatty alcohol content of <1.0%, and a free glucose content of <0.5%. 185.6 g of water (with a mass ratio of water to lauryl glucoside solution of 1:3.75) is added to the reaction vessel, and the temperature is raised to 77 °C at 280 rpm and stirred for 40 min until the mixture is homogeneous. Step S2: Add 34.03 g of solid superbase HND-63 (HND-63 to lauryl glucoside solution in a mass ratio of 1:20.45) to the reaction vessel in step S1 and react at 90 °C at 400 rpm for 2 h. After the reaction is complete, filter through a 200-mesh filter to remove solid particles. Step S3: Add 62.6 g of 1,3-dichloro-2-propanol (0.5 mol, molecular formula: C3H6Cl2O, Mn=128.98 g / mol) to the reaction vessel in step S2, heat to 93 °C at 180 rpm and react for 7.5 h. Monitor the conversion rate of the crosslinking agent until no residual amount is detected, and stop the reaction after the requirement is met. Step S4: Add 297.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, molecular formula: C3H6ClNaO4S, Mn=196.59 g / mol) to the reaction vessel in step S3, heat to 80 °C at 280 rpm and react for 4.5 h. Monitor the conversion rate of the sulfonating agent until no residual amount is detected. Stop the reaction after reaching the required level, cool to 17 °C, let stand for 16 h, filter through a 200-mesh filter, take the lauryl glucoside solution, freeze dry to obtain lauryl glucoside derivative (622.8 g).

[0039] The solid content was found to be 96%. HPLC analysis showed that the lauryl glucoside derivative content was 86%, nonionic matter was 10%, inorganic salts were 4.0%, and no residual crosslinking agent or sulfonating agent was detected. The calculated reaction yield of this example was 95.39%.

[0040] Comparative Example 1: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that sodium carbonate activator is not added in step S2, and water is used to make up the difference. The other steps are similar to those in Example 2.

[0041] The results showed that the reaction could proceed normally, but the final product, lauryl glucoside sulfonate derivative, was turbid, with low content and small molecular weight.

[0042] Comparative Example 2: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that the 167 g of hexaarm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) in step S3 is replaced with 167 g of water, and the other steps are similar to those in Example 2.

[0043] The results showed that the reaction could proceed normally, but the molecular weight of the final product, lauryl glucoside sulfonate derivative, was relatively small.

[0044] Comparative Example 3: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that the 167 g of hexaarm-polyethylene glycol chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) in step S3 is replaced with 42.8 g of hexaarm-polyethylene glycol chloride (6-ArmPEG-Cl, 0.0428 mol, Mn=1000 g / mol) and 124.2 g of water. The other steps are similar to those in Example 2.

[0045] The results showed that the reaction could proceed normally, but the molecular weight of the final product, lauryl glucoside sulfonate derivative, was relatively small.

[0046] Comparative Example 4: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that the 167 g of hexaarm-polyethylene glycol chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) in step S3 is replaced with 250 g of hexaarm-polyethylene glycol chloride (6-ArmPEG-Cl, 0.25 mol, Mn=1000 g / mol), and the other steps are similar to those in Example 2.

[0047] The results showed that the reaction could not proceed normally, with a large amount of insoluble matter forming and separation. The final product, lauryl glucoside sulfonate derivative, had a high residual cross-linking agent content.

[0048] Comparative Example 5: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that the 297.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) in step S4 is replaced with 297.9 g of water, and the other steps are similar to those in Example 2.

[0049] The results showed that the reaction could proceed normally, but lauryl glucoside sulfonate derivatives could not be obtained, and a large amount of insoluble matter was generated, resulting in layering.

[0050] Comparative Example 6: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that the 297.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) in step S4 is replaced with 198.59 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.0 mol, Mn=196.59 g / mol) and 99.31 g of water. The other steps are similar to those in Example 2.

[0051] The results showed that the reaction proceeded normally, but the content of the final product, lauryl glucoside sulfonate derivative, was low.

[0052] Comparative Example 7: Preparation of Lauryl Glucoside Sulfonate Derivatives The difference from Example 2 is that the 297.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) in step S4 is replaced with 595.77 g of sodium 3-chloro-2-hydroxypropanesulfonate (3.0 mol, Mn=196.59 g / mol), while the other steps are similar to those in Example 2.

[0053] The results showed that the reaction proceeded normally, with a significant amount of insoluble matter forming and the mixture separating into layers.

[0054] Example 1: Detection of Physicochemical Properties of Alkyl Glucoside Derivatives 1. Test method: The alkyl glucoside derivatives prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6 and 7 were subjected to physicochemical tests.

[0055] 2. Test Results: The experimental results are shown in Table 1.

[0056] Table 1. Results of Physicochemical Indicators sample Material status Solid content (%) Nonionic content (%) Active ingredient content (%) Inorganic salt content (%) Crosslinking agent residue (ppm) Sulfonating agent residue (%) Example 1 Uniform, transparent, and viscous 96 10 86 4.0 Not detected Not detected Example 2 Uniform, transparent, and viscous 98 8.0 90 3.5 Not detected Not detected Example 3 Uniform, transparent, and viscous 97 9.0 88 3.7 Not detected Not detected Example 4 Uniform, transparent, and viscous 96.5 7.0 87 3.8 Not detected Not detected Example 5 Uniform, transparent, and viscous 97 8.5 88 3.6 Not detected Not detected Example 6 Uniform, transparent, and viscous 98 8.0 90 3.0 Not detected Not detected Comparative Example 1 turbid and viscous 98 35 55 2.4 1200 3.2 Comparative Example 2 Uniform, transparent, and viscous 96 15 77 3.5 / 0.69 Comparative Example 3 Uniform, transparent, and viscous 97 11 82 2.2 / Not detected Comparative Example 4 turbid and viscous 95 30 62 3.7 6500 2.2 Comparative Example 5 turbid and viscous 95 92 / 3.6 Not detected / Comparative Example 6 Uniform, transparent, and viscous 96 16 76 3.5 Not detected Not detected Comparative Example 7 turbid and viscous 98 6.5 87 5.5 Not detected 1.3 As shown in Table 1, Examples 1-6 of this invention all yielded good alkyl glucoside sulfonate derivatives with high sulfonate conversion rates and uniform, transparent final products. Comparative Example 1, without the addition of an activator, shows that it affects subsequent crosslinking and sulfonation reactions, resulting in low conversion rates and turbidity in the final product due to precipitation. Comparative Examples 2-4 investigated the effects of no crosslinking agent, insufficient crosslinking agent, and excessive crosslinking agent, respectively. All these effects affect sulfonation efficiency, leading to high nonionic content and low sulfonate content. Excessive crosslinking agent can prevent normal reaction, resulting in the formation of numerous insoluble substances and stratification. Comparative Examples 5-7 investigated the effects of no sulfonating agent, insufficient sulfonating agent, and excessive sulfonating agent, respectively. The results show that without the sulfonating agent, sulfonate derivatives cannot be obtained; insufficient sulfonating agent results in inadequate conversion rates; however, excessive sulfonating agent leads to the formation of numerous insoluble substances, stratification, turbidity in the final product, and a high residual amount of sulfonating agent.

[0057] Experimental Example 2: Determination of the molecular weight of alkyl glucoside derivatives 1. Test method: The molecular weights of the alkyl glucoside derivatives prepared in Examples 1, 2, 3, 4, 5, and 6 were determined using gel permeation chromatography (GPC, Waters Corporation, USA; model: Waters 1525 / 2414). Chromatographically pure THF solution was used as the mobile phase at a flow rate of 1.0 mL / min. The column was calibrated with a monodistributed polystyrene standard, and the test temperature was 30 °C. Lauryl glucoside was used as a control sample.

[0058] Experimental results: The experimental results are shown in Table 2.

[0059] Table 2. Molecular weight determination results sample Weight-average molecular weight (Mw, Da) Example 1 2657 Example 2 4502 Example 3 4351 Example 4 6521 Example 5 4218 Example 6 1123 lauryl glucoside 348 As the molecular weight increases beyond 500 Daltons, the absorption of the molecule by normal human skin decreases rapidly. This means that large-molecule surfactants are less likely to penetrate human skin, reducing their irritant properties.

[0060] As shown in Table 2, the molecular weight of the alkyl glucoside of the present invention is significantly increased after sulfonation modification, which helps to reduce transdermal permeability and also helps to form larger micelles, thus reducing skin irritation.

[0061] Experimental Example 3: Determination of Critical Micelle Concentration of Alkyl Glucoside Derivatives 1. Test method: The critical micelle concentrations of the alkyl glucoside derivatives prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6 and 7 were determined.

[0062] Fluorescence spectroscopy was used for determination. Pyrene is a strongly hydrophobic probe with very low solubility in water. In the presence of micelles and other macromolecular systems, pyrene preferentially dissolves in the internal hydrophobic regions of these aggregates. The fluorescence emission spectrum of pyrene solution exhibits five characteristic peaks. The relative intensities of the peaks differ in environments with different polarities. The ratio of the luminescence intensity of the first characteristic peak at 373 nm (I1) to the third characteristic peak at 384 nm (I3) (I1 / I3) is highly sensitive to the polarity of the environment, decreasing as the polarity of the environment decreases. The solubility of pyrene varies in surfactant solutions of different concentrations. When the surfactant concentration is low, almost all pyrene in the solution exists in the aqueous phase, and the value of I1 / I3 is similar to that of pyrene in water. When the solution concentration is greater than the critical micelle concentration (CMC), the solubility increases. cmcWhen micelles form, pyrene enters the hydrophobic region inside the micelles from the aqueous phase. The change in environmental polarity leads to a sudden change in the I1 / I3 value. By finding the abrupt change point through the curve of I1 / I3 versus surfactant concentration, the critical micelle concentration of the surfactant can be determined. cmc Lauryl glucoside was used as a control sample.

[0063] 2. Test Results The experimental results are shown in Table 3.

[0064] Table 3 Critical micelle concentration (CMC) cmc Test results sample (g / L) Example 1 0.0171 Example 2 0.0155 Example 3 0.0186 Example 4 0.0159 Example 5 0.0173 Example 6 0.0128 Comparative Example 1 0.0279 Comparative Example 2 0.0357 Comparative Example 3 0.0281 Comparative Example 4 0.0572 Comparative Example 5 0.0326 Comparative Example 6 0.0265 Comparative Example 7 0.0388 lauryl glucoside 0.0237 Critical micelle concentration (CMC) cmc The minimum concentration of surfactants required for micelle formation in water is called the micelle concentration (MPC). When the surfactant concentration exceeds this point, they transform from monomeric to micelle form, a change that affects the surfactant's mildness. When the surfactant concentration is below this point... cmc At this time, it mainly exists in monomeric form, which is more likely to penetrate the skin and may cause strong irritation. Reaching or exceeding... cmc Subsequently, the surfactant forms micelles, reducing the monomer concentration, which helps to reduce skin irritation. Therefore, cmc It is an important indicator for measuring the mildness of surfactants. Under the same conditions, cmc The lower the concentration, the more valuable it is, meaning that micelles can be formed at relatively low concentrations.

[0065] As shown in Table 3, compared with lauryl glucoside, the alkyl glucoside sulfonate derivatives prepared in Examples 1-6 of this invention have lower [specific properties / effects]. cmc Its surface chemical properties are more outstanding.

[0066] Experimental Example 4: Test of the micelle aggregation number of alkyl glucoside derivatives 1. Test method: The micellar aggregation number of the alkyl glucoside derivatives prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6, and 7 was determined. Lauryl glucoside was used as a control sample.

[0067] The steady-state fluorescence quenching method was used for determination. Pyrene (Py) was used as the fluorescent probe, and benzophenone (Q) was used as the fluorescence quencher. A saturated pyrene solution was used as the solvent to prepare a solution with a concentration of 5 times... cmc The surfactant solution was prepared in a pretreated volumetric flask, and a control sample of the same concentration without quencher was also prepared. All samples were ultrasonically dispersed and kept at a constant temperature of 25 °C in a water bath for 2 h before use.

[0068] Pretreatment of volumetric flasks: Prepare a benzophenone-methanol solution of a specific concentration, accurately transfer a measured amount into a volumetric flask, and dry the methanol with nitrogen gas to ensure the concentration C in the volumetric flask is achieved. Q =0.2 mmol·L⁻¹. The instrument excitation wavelength was set to 335 nm, and the fluorescence intensity was read at 373 nm. Assuming that pyrene and benzophenone molecules follow a Poisson distribution within the micelles, Nm can be calculated using the following formula: ; Where: I1, I0 -- fluorescence intensity of the sample at a wavelength of 373 nm with and without quencher; C Q --Concentration of the fluorescence quencher; S T --Total concentration of the surfactant solution.

[0069] 2. Test Results: The experimental results are shown in Table 4.

[0070] Table 4. Test results of Nm (micelle aggregation number) sample Nm (micelle aggregation number) Example 1 82 Example 2 85 Example 3 78 Example 4 81 Example 5 76 Example 6 84 Comparative Example 1 45 Comparative Example 2 67 Comparative Example 3 74 Comparative Example 4 47 Comparative Example 5 38 Comparative Example 6 71 Comparative Example 7 73 lauryl glucoside 36 Micelle aggregation number refers to the minimum number of surfactant molecules required to form micelles when a certain concentration of surfactant molecules is reached in a solution. Micelle formation is an important characteristic of surfactants, affecting their performance in various applications such as detergents, emulsifiers, and dispersers.

[0071] As shown in Table 4, compared with lauryl glucoside, the alkyl glucoside sulfonate derivatives prepared in Examples 1-6 of this invention have a larger micelle aggregation number and larger micelle size, making them less likely to penetrate into the stratum corneum of the skin, which corresponds to their higher mildness.

[0072] Test Example 5: Safety Testing of Alkyl Glucoside Derivatives 1. Test method: 1.1 Stimulation Test: The irritant properties of the alkyl glucoside derivatives prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6, and 7 were determined using the zein method. Lauryl glucoside was used as a control sample.

[0073] 1.2 Toxicity Performance Test: The alkyl glucoside derivatives prepared in Example 2 were selected for toxicological performance testing.

[0074] 2. Test Results: The experimental results are shown in Tables 5 and 6.

[0075] 2.1 The results of the irritation test are shown in Table 5.

[0076] Table 5. Results of Stimulation Tests sample Zein value (g / L) Example 1 0.0195 Example 2 0.0183 Example 3 0.0212 Example 4 0.0197 Example 5 0.0205 Example 6 0.0233 Comparative Example 1 0.0357 Comparative Example 2 0.0286 Comparative Example 3 0.0275 Comparative Example 4 0.0349 Comparative Example 5 0.0767 Comparative Example 6 0.0331 Comparative Example 7 0.0746 lauryl glucoside 0.0890 Zein, which is almost completely insoluble in water, interacts with surfactants, increasing its water solubility. Stronger irritants dissolve zein more readily than weaker irritants. Therefore, by measuring the change in nitrogen content in aqueous solution before and after surfactant interaction, the solubility of zein after surfactant interaction can be determined. The nitrogen content in the dissolved zein is directly proportional to the skin irritation caused by the surfactant, thus revealing the degree of surfactant irritation.

[0077] As shown in Table 5, the alkyl glucoside sulfonate derivatives prepared in Examples 1-6 of this invention have low irritation.

[0078] 2.2 The results of the toxicity test are shown in Table 6.

[0079] Table 6 Toxicity Performance Test Results Serial Number project Test Results 1 Acute skin irritation test Non-irritating 2 Skin allergy test No skin allergic reaction observed 3 Skin phototoxicity test No skin phototoxicity observed 4 Skin photoallergy test The sensitization rate was 0%, the sensitization level was I, and the sensitization intensity was weak. 5 Bacterial reverse mutation assay Negative 6 In vitro mammalian cell chromosome aberration assay Negative 7 Acute percutaneous toxicity test <![CDATA[LD 50 >2500 mg / kg]]> 8 28-day repeated-dose percutaneous toxicity test NOAEL value: 1000 mg / kg BW / d Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. An alkyl glucoside derivative, characterized in that, The alkyl glucoside derivative is shown in Formula I: Formula I; Among them, the R1 group is or The R2 group is Or H; or the same as the R1 group; x=1~4, y=1~10, z=1~3, R is C8-C 20 alkyl groups.

2. The alkyl glucoside derivative as described in claim 1, characterized in that, When x=1, R2 is H; R1 is Where z = 1~3, and R is C8-C 20 alkyl groups.

3. The alkyl glucoside derivative as described in claim 1, characterized in that, When x = 2~4, R1 = R2, specifically... Where y = 1~10, z = 1~3, and R is C8-C 20 alkyl groups.

4. A method for preparing an alkyl glucoside derivative, characterized in that, Includes the following steps: Step S1: Add the alkyl glucoside solution and solvent to the reaction vessel, heat to 75-85 °C at 200-400 rpm, and stir for 30-60 min; Step S2: Add the activator to the reaction vessel from step S1 and react. Heat the mixture to 85-90 °C at a rate of 400-600 rpm and react for 1-2 h. Step S3: Add the crosslinking agent to the reaction vessel in step S2 to carry out the reaction, monitor the conversion rate, and stop the reaction after the requirement is reached; Step S4: Add the sulfonating agent to the reaction vessel in step S3 and react. Monitor the conversion rate and stop the reaction when the required conversion rate is reached. Cool to 15~20 ℃, let stand for 12~24 h, filter, take the filtrate, dry under reduced pressure, and remove the solvent to obtain the final product.

5. The method for preparing the alkyl glucoside derivative as described in claim 4, characterized in that, The alkyl glucoside in step S1 is C 12 -C 16 Alkyl glucoside, C 12 -C 18 Alkyl glucoside, C 12 -C 20 Alkyl glucoside, C8-C 14 One or more of alkyl glucoside, octyl glucoside, decyl glucoside, octyl / decyl glucoside, lauryl glucoside, myristyl glucoside, and cocoyl glucoside; wherein the mass ratio of the alkyl glucoside solution to the solvent is (1.5~5):

1.

6. The method for preparing the alkyl glucoside derivative as described in claim 4, characterized in that, The solvent in step S1 is at least one of water, methanol, ethanol, isopropanol, acetone, and tetrahydrofuran; or a mixture of water and an organic solvent.

7. The method for preparing the alkyl glucoside derivative as described in claim 4, characterized in that, The activator is one of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium carbonate, potassium carbonate, and solid superbase catalyst, and the mass ratio of the activator to the alkyl glucoside solution is 1:(15~30).

8. The method for preparing the alkyl glucoside derivative as described in claim 4, characterized in that, In step S3, the crosslinking agent is multi-arm polyethylene glycol chloride or 1,3-dichloro-2-propanol, and the molar ratio of the crosslinking agent to the alkyl glucoside is (0.2~0.3):

1. The temperature is increased to 90~95 °C at a speed of 100~200 rpm, and the reaction is carried out for 6~8 h.

9. The method for preparing the alkyl glucoside derivative as described in claim 8, characterized in that, The structure of the multi-arm polyethylene glycol chloride is as follows: Where m=2~6; n=1~3; molecular weight 0.4~2 K.

10. The method for preparing the alkyl glucoside derivative as described in claim 4, characterized in that, The sulfonating agent in step S4 is one of sodium 2-chloroethylsulfonate, sodium 3-chloro-2-hydroxypropanesulfonate, and sodium 4-chloro-1-hydroxybutanesulfonate. The molar ratio of the sulfonating agent to the alkyl glucoside is (1.2~2.0):

1. The temperature is increased to 80~85 °C at a speed of 200~400 rpm, and the reaction is carried out for 3~5 h.

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