Alkyl glycoside sulfonate and method of making and use thereof

Abstract

The application belongs to the technical field of daily chemicals, and particularly relates to a high-temperature and mild alkyl glucoside sulfonate as well as a preparation method and application thereof. The alkyl glucoside sulfonate provided by the application is obtained by using the hydroxyl activity on the glucose unit of glucoside to perform chemical modification, and specifically, the alkyl glucoside is first subjected to intramolecular cross-linking by using 1,3-dichloro-2-propanol, and then subjected to anionization modification by using 3-chloro-2-hydroxypropanesulfonate sodium. The alkyl glucoside sulfonate prepared by the application has the advantages of mildness, low irritation, strong hard water resistance, good foaming performance, low skin penetration and small residual amount, can effectively solve the defects of strong penetration, strong deproteinization and delipidation, great damage to skin barrier and weak thickening effect of alkyl glucoside in personal cleaning products, and is very suitable for being widely used and popularized in daily chemicals.

Description

Technical Field

[0001] This invention belongs to the field of daily chemical products technology, specifically relating to a high-temperature and volatile alkyl glycoside sulfonate, its preparation method, and its application. Background Technology

[0002] In daily life, people frequently come into contact with cleaning products. Surfactants in these products can easily disrupt the orderly structure of the lipid layer during the cleaning process through hydrophobic interactions, leading to the dissolution or imbalance of key lipids such as ceramides, causing "leakage" of the stratum corneum. Therefore, the gentleness of surfactants in cleaning products is crucial for maintaining a healthy skin barrier.

[0003] Among numerous mild surfactants, alkyl glucosides (APGs) stand out as a highly distinctive and promising surfactant. APGs are rapidly gaining popularity in detergents, cosmetics, and food due to their biodegradability and low toxicity. However, despite their overall excellent performance, APGs also have some limitations, primarily: their nonionic structure results in relatively high permeability and strong deproteinizing / degreasing capabilities, which can damage the skin barrier, leaving a slippery feeling after washing and causing significant dryness, especially in autumn and winter. APG derivatives, through structural modification, can achieve targeted performance enhancements, effectively increasing the application value of APGs.

[0004] Patent document CN105418697A discloses an alkyl glycoside sulfonate surfactant, its preparation method, and its application. The preparation method involves using a mixed solvent of water and isopropanol, adding an alkaline substance to conduct an alkalization reaction to obtain an intermediate system; then adding sodium 3-chloro-2-hydroxypropanesulfonate or potassium 3-chloro-2-hydroxypropanesulfonate to the intermediate system for an etherification reaction. The yield of the obtained alkyl glycoside sulfonate is 30.2%–45.3%, and its application focuses on oilfield development, addressing the stability issues of traditional surfactants in acidic environments.

[0005] Patent document CN105646606A discloses an alkyl glycoside sulfonate and its synthesis method. This method involves reacting epichlorohydrin with sodium bisulfite to generate a sodium 3-chloro-2-hydroxypropyl sulfonate intermediate, improving reaction controllability. The sodium 3-chloro-2-hydroxypropyl sulfonate intermediate and a long-chain alkyl glycoside are then added to a reactor, where a condensation reaction occurs in the organic solvent DMF in the presence of a K₂CO₃ alkaline catalyst. The yield of the obtained alkyl glycoside sulfonate is as high as 88.05%, which is superior to traditional methods.

[0006] However, current research on APG sulfonate derivatives mainly focuses on solvent synthesis. While this method can achieve high conversion rates, the solvent removal process is energy-intensive and inevitably leaves solvent residues, especially the highly polar solvent DMF, which poses significant safety risks and is unsuitable for use in everyday chemicals. Aqueous solvent synthesis, on the other hand, suffers from relatively low conversion rates and difficulties in separating the sulfonating agent from the reactants and products, causing numerous inconveniences for practical applications. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention provides a high-temperature and volatile alkyl glucoside sulfonate, its preparation method, and its application in personal care products. The alkyl glucoside sulfonate provided by this invention is obtained through chemical modification utilizing the hydroxyl activity of the glucoside unit. The resulting alkyl glucoside sulfonate exhibits advantages such as mildness, low irritation, strong hard water resistance, excellent foaming ability over a wide pH range, and low skin penetration and residue, making it suitable for widespread use and promotion in daily chemical products.

[0008] The technical solution of the present invention is as follows:

[0009] This invention provides a high-temperature and reactive alkyl glycoside sulfonate, which is shown in Formula I:

[0010] Formula I;

[0011] Where a = 1~3, R is C8- 20 alkyl.

[0012] Furthermore, the C8- 20 Alkyl groups are 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 Lauroside C 12 Myristyl C14 Coconut oil-based C8-C 18 One or more of them.

[0013] Furthermore, the present invention also provides a method for preparing high-temperature and alkyl glycoside sulfonate, comprising the following steps:

[0014] Step S1: Add the alkyl glucoside solution to the reaction vessel, stir at 200-400 rpm and heat to 75-85 °C;

[0015] Step S2: Add the solid superbase to the reaction vessel in step S1 to carry out the reaction. After the reaction is completed, separate the solid superbase.

[0016] Step S3: Add 1,3-dichloro-2-propanol to the reaction vessel from step S2 and react, monitor the conversion rate, and stop the reaction when the required conversion rate is reached.

[0017] Step S4: Add sodium 3-chloro-2-hydroxypropanesulfonate 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 °C, let stand for 48-72 h, and filter to obtain the final product.

[0018] 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 The alkyl glucoside is selected from one or more of the following: alkyl glucoside, octyl glucoside, decyl glucoside, octyl / decyl glucoside, lauryl glucoside, myristyl glucoside, and cocoyl glucoside; wherein the mass ratio of alkyl glucoside to water in the alkyl glucoside solution is 50:50, and the free fatty alcohol content is <1.0% and the free glucose content is <0.5%.

[0019] Furthermore, the solid superalkali in step S2 is one of HND-61, HND-62, HND-63 and HND-64, which is obtained by supporting potassium carbonate on activated alumina and then sintering.

[0020] Furthermore, in step S2, the mass ratio of the solid superbase to the alkyl glucoside is 1:(10~30).

[0021] Further, the reaction conditions in step S2 are: a stirring speed of 400-600 rpm and a temperature of 85-90℃ for 1-2 hours. The solid superalkali separation methods in step S2 include, but are not limited to, centrifugation, filtration, vacuum filtration, and pressure filtration; preferably, filtration is done through a 200-mesh filter.

[0022] Further, in step S3, the molar ratio of 1,3-dichloro-2-propanol to alkyl glucoside is (0.4~0.6):1. The purity of the 1,3-dichloro-2-propanol is ≥99%.

[0023] Furthermore, the reaction conditions in step S3 are: a stirring speed of 100-200 rpm and a temperature of 90-95℃ for 6-8 h.

[0024] Furthermore, the conversion rate of 1,3-dichloro-2-propanol in step S3 is monitored by HPLC, and the residual amount is ≤0.1ppm (detection concentration 0.005ppm, minimum quantitative concentration 0.025ppm).

[0025] Furthermore, in step S4, the molar ratio of sodium 3-chloro-2-hydroxypropanesulfonate to alkyl glucoside is (1~2):1, and the purity of sodium 3-chloro-2-hydroxypropanesulfonate is ≥99%.

[0026] Furthermore, the reaction conditions in step S4 are: a stirring speed of 200-400 rpm and a temperature of 80-85°C for 6-8 h.

[0027] Furthermore, the conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate in step S4 is monitored by HPLC, and the residual amount is ≤0.1% (detection concentration 0.1%, minimum quantitative concentration 0.1%).

[0028] In addition, the present invention also provides the application of the aforementioned high-temperature and reactive alkyl glycoside sulfonate in cleaning products. The cleaning products are personal care products, including but not limited to shampoos, bath products, facial cleansers, etc.

[0029] The high-temperature and reactive alkyl glycoside sulfonate provided by this invention utilizes the hydroxyl activity of the glucosinolate unit for chemical modification. First, it undergoes intramolecular cross-linking with a 1,3-dichloro-2-propanol cross-linking agent, followed by anionization modification with sodium 3-chloro-2-hydroxypropanesulfonate. The alkyl glycoside sulfonate prepared by this invention has advantages such as high mildness, low irritation, low residue, strong hard water resistance, and good foaming performance. It effectively solves the defects of alkyl glucosides in personal care products, such as strong permeability, strong deproteinization and degreasing ability, significant damage to the skin barrier, and weak thickening effect. This effectively expands the application of alkyl glucosides, especially suitable for products with high mildness requirements, such as baby products and facial cleansers. Furthermore, the high-temperature and reactive alkyl glycoside sulfonate preparation method provided by this invention also has the advantages of high yield (over 95%), simple operation, and high reproducibility, which is conducive to the promotion and application of this alkyl glycoside sulfonate preparation process.

[0030] In summary, compared with the prior art, the high-temperature and alkyl glycoside sulfonate provided by the present invention has the following advantages:

[0031] (1) The alkyl glucoside sulfonate provided by the present invention has the advantages of high mildness, low irritation, low residue and easy washing. It can effectively solve the defects of alkyl glucoside in personal cleaning products, such as strong deproteinization / degreasing ability, high irritation and large residue. It can effectively expand the application of alkyl glucoside.

[0032] (2) The method for preparing alkyl glucoside sulfonate provided by the present invention uses water as a solvent, which is environmentally friendly and leaves no harmful residues. Moreover, the process has the advantages of high yield (over 95%), simple operation, and high repeatability, which is conducive to the large-scale promotion and application of the production process. Attached Figure Description

[0033] Figure 1 The Zein value diagram is shown for the combination of SDS and lauryl glucoside sulfonate prepared in Example 2.

[0034] Figure 2 The graph shows the foaming capacity of lauryl glucoside sulfonate prepared in Example 2 in pure water and hard water at different pH values. Detailed Implementation

[0035] 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.

[0036] Example 1: Preparation of coconut oil glucoside sulfonate

[0037] Step S1: Add 696 g of cocoyl glucoside solution (1.0 mol, Mn=348 g / mol based on cocoyl glucoside) to the reaction vessel. The cocoyl glucoside solution is a mixture of cocoyl glucoside and water, wherein the mass ratio of cocoyl glucoside to water is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%. Stir at 200 rpm and heat to 75 °C.

[0038] Step S2: Add 17.4 g of HND-61 solid superbase (HND-61 to cocoyl glucoside mass ratio of 1:20) to the reaction vessel in step S1, stir and heat to 85 °C at 400 rpm for 1 h, filter through a 200 mesh screen to remove HND-61 solid superbase.

[0039] Step S3: Add 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) to the reaction vessel in step S2, stir at 100 rpm and heat to 90 °C for 6 h. Monitor the conversion rate of 1,3-dichloro-2-propanol by HPLC until the residual amount is 0.1 ppm. Stop the reaction after the requirement is met.

[0040] Step S4: 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) was added to the reaction vessel in step S3. The mixture was stirred at 200 rpm and 80 °C for 3 h. The conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate was monitored by HPLC until no residue was detected. The mixture was then cooled to 15 °C and allowed to stand for 24 h. The mixture was then filtered through a 200-mesh filter to obtain cocoyl glucoside sulfonate (994.8 g).

[0041] The solid content was found to be 62%. HPLC analysis showed that the content of cocoyl glucoside sulfonate was 50.5%. GPC analysis showed that the weight-average molecular weight was 1056 Da, nonionic matter was 6.8%, inorganic salts were 4.4%, and the residues of 1,3-dichloro-2-propanol and sodium 3-chloro-2-hydroxypropanesulfonate were not detected. The calculated reaction yield of this example was 95.15%.

[0042] Example 2: Preparation of lauryl glucoside sulfonate

[0043] Step S1: Add 696 g of lauryl glucoside solution (1.0 mol, calculated as lauryl glucoside, Mn=348 g / mol) to the reaction vessel. The lauryl glucoside solution is a mixture of lauryl glucoside and water, wherein the mass ratio of lauryl glucoside to water is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%. Stir at 300 rpm and heat to 80 °C.

[0044] Step S2: Add 17.4 g of HND-62 solid superbase (HND-62 to lauryl glucoside mass ratio of 1:20) to the reaction vessel in step S1, stir and heat to 90 °C at 500 rpm for 2 h, filter through a 200 mesh screen to remove HND-62 solid superbase.

[0045] Step S3: Add 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) to the reaction vessel in step S2, stir and heat to 92 °C at 150 rpm for 7 h, monitor the conversion rate of 1,3-dichloro-2-propanol by HPLC until the residual amount is undetectable, and stop the reaction after the requirement is met;

[0046] Step S4: 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) was added to the reaction vessel in step S3. The mixture was stirred at 300 rpm and 82 °C for 4 h. The conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate was monitored by HPLC until no residue was detected. The mixture was then cooled to 16 °C and allowed to stand for 72 h. The mixture was then filtered through a 200-mesh filter to obtain lauryl glucoside sulfonate (1048.3 g).

[0047] The solid content was 61.5%, and the lauryl glucoside sulfonate content was 51.2% according to HPLC analysis. The weight-average molecular weight was 1088 Da according to GPC analysis. The nonionic content was 6.3%, the inorganic salt content was 4.12%, and the residues of 1,3-dichloro-2-propanol and sodium 3-chloro-2-hydroxypropanesulfonate were not detected. The calculated reaction yield of this example was 98.66%.

[0048] Example 3: Preparation of lauryl glucoside sulfonate

[0049] Step S1: Add 696 g of lauryl glucoside solution (1.0 mol, calculated as lauryl glucoside, Mn=348 g / mol) to the reaction vessel. The lauryl glucoside solution is a mixture of lauryl glucoside and water, wherein the mass ratio of lauryl glucoside to water is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%. Stir at 250 rpm and heat to 80 °C.

[0050] Step S2: Add 26.8 g of HND-63 solid superbase (HND-63 to lauryl glucoside mass ratio of 1:13) to the reaction vessel in step S1, stir and heat to 85 °C at 400 rpm for 1 h, filter through a 200 mesh screen to remove HND-63 solid superbase.

[0051] Step S3: Add 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) to the reaction vessel in step S2, stir and heat to 95 °C at 200 rpm for 8 h, monitor the conversion rate of 1,3-dichloro-2-propanol by HPLC until no residual amount is detected, and stop the reaction after the requirement is met;

[0052] Step S4: 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) was added to the reaction vessel in step S3. The mixture was stirred at 250 rpm and 85 °C for 5 h. The conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate was monitored by HPLC until the residual amount was 0.1%. The mixture was then cooled to 20 °C and allowed to stand for 36 h. The mixture was then filtered through a 200-mesh filter to obtain lauryl glucoside sulfonate (1038.7 g).

[0053] The solid content was 62.2%, and the lauryl glucoside sulfonate content was 52.3% according to HPLC analysis. The weight-average molecular weight was 1121 Da according to GPC analysis. The nonionic content was 6.4%, the inorganic salt content was 4.02%, and the residues of 1,3-dichloro-2-propanol and sodium 3-chloro-2-hydroxypropanesulfonate were not detected. The calculated reaction yield of this example was 96.92%.

[0054] Example 4, C8-C 14 Preparation of alkyl glucoside sulfonates

[0055] Step S1: Take 640 g of C8-C 14 Alkyl glucoside solution (1.0 mol, in C8-C) 14 (Calculated as alkyl glucoside, Mn=320 g / mol) is added to the reaction vessel, wherein the C8-C 14Alkyl glucoside solution is C8-C 14 A mixture of alkyl glucoside and water, wherein C8-C 14 The mass ratio of alkyl glucoside to water was 50:50, the free fatty alcohol content was <1.0%, and the free glucose content was <0.5%; the mixture was stirred at 400 rpm and heated to 75 °C.

[0056] Step S2: Mix 26.8 g of HND-64 solid superalkali (HND-64 and C8-C) 14 The alkyl glucoside (mass ratio 1:13) was added to the reaction vessel in step S1, stirred at 450 rpm and heated to 88 °C for 1.5 h, filtered through a 200-mesh filter to remove the HND-64 solid superbase.

[0057] Step S3: Add 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) to the reaction vessel in step S2, stir at 120 rpm and heat to 91 °C for 6.5 h. Monitor the conversion rate of 1,3-dichloro-2-propanol by HPLC until the residual amount is 0.1 ppm, and stop the reaction after the requirement is met.

[0058] Step S4: Add 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) to the reaction vessel from step S3. Stir the mixture at 400 rpm and 81 °C for 3.5 h. Monitor the conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate by HPLC until the residual amount reaches 0.01%. Cool the mixture to 18 °C and let it stand for 24 h. Filter the mixture through a 200-mesh screen to obtain C8-C. 14 Alkyl glucoside sulfonate (981.3 g).

[0059] Testing revealed a solid content of 61.6%, and HPLC analysis showed that it contained C8-C... 14 The alkyl glucoside sulfonate content was 50.8%, and its weight-average molecular weight was 1045 Da as determined by GPC. The nonionic content was 6.8%, the inorganic salt content was 4.08%, and the residues of 1,3-dichloro-2-propanol and sodium 3-chloro-2-hydroxypropanesulfonate were not detected. The reaction yield of this example was calculated to be 95.41%.

[0060] Example 5: Preparation of Octyl / Decyl Glucoside Sulfonate

[0061] Step S1: Add 814 g of octyl / decyl glucoside solution (1.0 mol, Mn = 407 g / mol based on octyl / decyl glucoside) to a reaction vessel. The octyl / decyl glucoside solution is a mixture of octyl / decyl glucoside and water, wherein 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%. Stir at 350 rpm and heat to 80 °C.

[0062] Step S2: Add 26.8 g of HND-62 solid superbase (HND-62 to octyl / decyl glucoside mass ratio of 1:18.75) to the reaction vessel in step S1, stir and heat to 85 °C at 550 rpm for 1.2 h, filter through a 200 mesh screen to remove HND-62 solid superbase;

[0063] Step S3: Add 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) to the reaction vessel in step S2, stir at 160 rpm and heat to 94 °C for 7 h. Monitor the conversion rate of 1,3-dichloro-2-propanol by HPLC until the residual amount is 0.05 ppm, and stop the reaction after the requirement is met.

[0064] Step S4: 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) was added to the reaction vessel in step S3. The mixture was stirred at 350 rpm and 84 °C for 4 h. The conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate was monitored by HPLC until no residue was detected. The mixture was then cooled to 19 °C and allowed to stand for 72 h. The mixture was then filtered through a 200-mesh filter to obtain octyl / decyl glucoside sulfonate (1123.8 g).

[0065] The solid content was 62.4%, and the octyl / decyl glucoside sulfonate content was 51.7% according to HPLC analysis. The weight average molecular weight was 1212 Da according to GPC analysis. The nonionic content was 6.6%, the inorganic salt content was 4.17%, and the residues of 1,3-dichloro-2-propanol and sodium 3-chloro-2-hydroxypropanesulfonate were not detected. The reaction yield of this example was calculated to be 95.88%.

[0066] Example 6, C 12 -C 16 Preparation of alkyl glucoside sulfonates

[0067] Step S1: Take 696 g of C 12 -C 16 Alkyl glucoside solution (1.0 mol, at C 12 -C16 (Calculated as alkyl glucoside, Mn = 348 g / mol) was added to the reaction vessel, and the C... 12 -C 16 Alkyl glucoside solution is C 12 -C 16 A mixture of alkyl glucoside and water, wherein C 12 -C 16 The mass ratio of alkyl glucoside to water was 50:50, the free fatty alcohol content was <1.0%, and the free glucose content was <0.5%; the mixture was stirred at 280 rpm and heated to 77 °C.

[0068] Step S2: Mix 26.8 g of HND-61 solid superalkali (HND-61 and C) 12 -C16 alkyl glucoside (mass ratio 1:16) was added to the reaction vessel in step S1, stirred at 400 rpm and heated to 90 °C for 2 h, filtered through a 200-mesh filter to remove HND-61 solid superbase.

[0069] Step S3: Add 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) to the reaction vessel in step S2, stir and heat to 93 °C at 180 rpm for 7.5 h, monitor the conversion rate of 1,3-dichloro-2-propanol by HPLC until the residual amount is undetectable, and stop the reaction after the requirement is met;

[0070] Step S4: Add 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) to the reaction vessel from step S3. Stir the mixture at 280 rpm and 80 °C for 4.5 h. Monitor the conversion rate of sodium 3-chloro-2-hydroxypropanesulfonate by HPLC until no residue is detected. Cool the mixture to 17 °C and let it stand for 36 h. Filter the mixture through a 200-mesh screen to obtain C. 12 -C 16 Alkyl glucoside sulfonate (1014.1 g).

[0071] Testing revealed a solid content of 61.8%, and HPLC analysis showed that C... 12 -C 16 The alkyl glucoside sulfonate content was 50.3%, and its weight-average molecular weight was 1064 Da as determined by GPC. The nonionic content was 6.95%, the inorganic salt content was 4.27%, and the residues of 1,3-dichloro-2-propanol and sodium 3-chloro-2-hydroxypropanesulfonate were not detected. The reaction yield of this example was calculated to be 95.88%.

[0072] Comparative Example 1: Preparation of Lauryl Glucoside Sulfonate

[0073] The difference from Example 2 is that HND-62 solid superalkali 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.

[0074] The results showed that the reaction could proceed normally, but the final product, lauryl glucoside sulfonate, was turbid, indicating a low degree of reaction.

[0075] Comparative Example 2: Preparation of Lauryl Glucoside Sulfonate

[0076] The difference from Example 2 is that 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) in step S3 is replaced with 64.5 g of water, and the other steps are similar to those in Example 2.

[0077] The results showed that the reaction could proceed normally, but the final product, lauryl glucoside sulfonate, had a small molecular weight and a low degree of reaction. GPC analysis showed that its weight-average molecular weight was 540 Da.

[0078] Comparative Example 3: Preparation of Lauryl Glucoside Sulfonate

[0079] The difference from Example 2 is that the 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) in step S3 is replaced with 25.8 g of 1,3-dichloro-2-propanol (0.2 mol, Mn=128.99 g / mol) and 38.7 g of water, while the other steps are similar to those in Example 2.

[0080] The results showed that the reaction proceeded normally, but the molecular weight of the final product, lauryl glucoside sulfonate, was relatively small. GPC analysis showed that its weight-average molecular weight was 605 Da.

[0081] Comparative Example 4: Preparation of Lauryl Glucoside Sulfonate

[0082] The difference from Example 2 is that the 64.5 g of 1,3-dichloro-2-propanol (0.5 mol, Mn=128.99 g / mol) in step S3 is replaced with 90.3 g of 1,3-dichloro-2-propanol (0.7 mol, Mn=128.99 g / mol), while the other steps are similar to those in Example 2.

[0083] 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, had a high residual amount of 1,3-dichloro-2-propanol.

[0084] Comparative Example 5: Preparation of Lauryl Glucoside Sulfonate

[0085] The difference from Example 2 is that the 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) in step S4 is replaced with 294.9 g of water, and the other steps are similar to those in Example 2.

[0086] The results showed that the reaction could proceed normally, but lauryl glucoside sulfonate could not be obtained, and a large amount of insoluble matter was generated, resulting in layering.

[0087] Comparative Example 6: Preparation of Lauryl Glucoside Sulfonate

[0088] The difference from Example 2 is that the 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) in step S4 is replaced with 147.4 g of sodium 3-chloro-2-hydroxypropanesulfonate (0.75 mol, Mn=196.59 g / mol) and 147.5 g of water. The other steps are similar to those in Example 2.

[0089] The results showed that the reaction proceeded normally, but the content of the final product, lauryl glucoside sulfonate, was low.

[0090] Comparative Example 7: Preparation of Lauryl Glucoside Sulfonate

[0091] The difference from Example 2 is that the 294.9 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.5 mol, Mn=196.59 g / mol) in step S4 is replaced with 368.6 g of sodium 3-chloro-2-hydroxypropanesulfonate (1.875 mol, Mn=

[0092] (196.59 g / mol), the other steps are similar to those in Example 2.

[0093] The results showed that the reaction proceeded normally, with a significant amount of insoluble matter forming and the mixture separating into layers.

[0094] Test Example 1: Mildness Test of Alkyl Glucoside Sulfonate

[0095] 1. Test method:

[0096] 1.1 Single-sample irritation test:

[0097] The irritant properties of alkyl glycoside sulfonates 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, with lauryl glucoside as a control sample.

[0098] 1.2. Synergistic Reduction of Irritation Test:

[0099] Using SDS (sodium dodecyl sulfate) as a reference, the effect of SDS combined with lauryl glucoside sulfonate prepared in Example 2 on irritation was determined by the zein method.

[0100] 2. Test Results

[0101] 2.1 The results of the single sample irritation test are shown in Table 1.

[0102] Table 1. Results of Irritation Tests on Single Samples

[0103] 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

[0104] Zein, which is almost completely insoluble in water, interacts with surfactants, increasing its water solubility. Stronger, more irritating surfactants dissolve zein more readily than weaker, irritating surfactants; that is, the nitrogen content in the dissolved zein is directly proportional to the skin irritation caused by the surfactant. As shown in Table 1, the alkyl glycoside sulfonate prepared in this invention has low skin irritation and high mildness.

[0105] 2.2, Results of the synergistic reduction of irritation test, such as Figure 1 As shown.

[0106] Figure 1 The Zein value diagram is shown for the combination of SDS and lauryl glucoside sulfonate prepared in Example 2.

[0107] Depend on Figure 1 It can be seen that the lauryl glucoside sulfonate prepared in Example 2 has a good synergistic effect with SDS in reducing irritation.

[0108] Experimental Example 2: Foaming Performance Test of Alkyl Glucoside Sulfonate

[0109] 1. Test method:

[0110] 1.1 Foam Performance Test:

[0111] The foaming ability of the alkyl glycoside sulfonates prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6 and 7 in pure water and hard water was investigated using a Roche foam analyzer, with lauryl glucoside as the control sample.

[0112] 1.2 Foaming performance test at different pH values:

[0113] The foaming ability of lauryl glucoside sulfonate prepared in Example 2 was investigated using a Roche foam apparatus in pure water and hard water at different pH values.

[0114] Experimental results:

[0115] 2.1 The foam performance test results are shown in Table 2.

[0116] Table 2 Foam Performance Test Results

[0117] sample pure water Hard water (150 mg / L) Example 1 160~155 145~140 Example 2 155~150 140~140 Example 3 150~150 140~135 Example 4 155~150 140~135 Example 5 165~160 150~145 Example 6 155~150 145~140 Comparative Example 1 120~115 105~100 Comparative Example 2 140~135 120~115 Comparative Example 3 140~140 115~110 Comparative Example 4 135~130 110~105 Comparative Example 5 120~115 105~100 Comparative Example 6 135~130 110~105 Comparative Example 7 115~110 95~90 lauryl glucoside 110~105 85~80

[0118] 2.2. Test results of foaming performance at different pH values ​​are as follows: Figure 2 As shown.

[0119] Figure 2 The graph shows the foaming capacity of lauryl glucoside sulfonate prepared in Example 2 in pure water and hard water at different pH values.

[0120] From Table 2 and Figure 2 It is known that the alkyl glucoside sulfonate prepared by this invention has good foaming ability, a certain degree of hard water resistance, and good foaming ability over a wide pH range.

[0121] Test Example 3: Residual Performance Test of Alkyl Glucoside Sulfonate

[0122] 1. Test method:

[0123] The residues of alkyl glycoside sulfonates prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6 and 7 were determined.

[0124] The inner fixation area of ​​the forearm was treated with a solution of alkyl glycoside sulfonate surfactant prepared in Examples 1, 2, 3, 4, 5, 6, Comparative Examples 1, 2, 3, 4, 5, 6, and 7 at a concentration of 0.5% for 2 min, rinsed with deionized water, and dried. A cotton pad soaked in a concentration of 1% indigo carmine solution was then applied for 2 min, rinsed with deionized water, and dried. The ΔE*ab value of the treated area was measured using a colorimeter. ΔE*ab represents the total color difference; a larger value indicates a greater difference from the initial color and less stimulation. Each sample was tested in parallel with 6 groups, and the average value was taken. Lauryl glucoside, sodium lauroyl sarcosinate, and SDS were used as control samples.

[0125] 2. Test Results

[0126] The experimental results are shown in Table 3.

[0127] Table 3 Residual performance test results

[0128] sample ΔE*ab average value Example 1 16.36 Example 2 17.28 Example 3 15.74 Example 4 16.02 Example 5 17.11 Example 6 17.53 Comparative Example 1 12.34 Comparative Example 2 13.72 Comparative Example 3 14.38 Comparative Example 4 14.21 Comparative Example 5 12.88 Comparative Example 6 15.17 Comparative Example 7 15.26 lauryl glucoside 12.57 Sodium lauroyl sarcosinate 13.59 SDS 5.26

[0129] As shown in Table 3, compared with SDS, lauryl glucoside, and sodium lauroyl sarcosinate, the alkyl glucoside sulfonates prepared in Examples 1-6 of this invention have significantly lower residue levels on the skin. This indicates that the anionization modification of the sulfonate improves the nonionic water solubility of the glycoside, reduces its residue on the skin, and indirectly proves its milder properties.

[0130] Application Example 1: 2-in-1 Baby Wash and Bath

[0131] Table 4 2-in-1 Baby Shampoo and Bath Formula

[0132]

[0133] Preparation method:

[0134] Step 1: Mix and stir component A, then heat to 80~85 ℃ to obtain mixture I;

[0135] Step 2: Add component B to mixture I sequentially and stir until homogeneous to obtain mixture II;

[0136] Step 3: Cool mixture II to 60~65 ℃, add glyceryl oleate, stir until uniform, then cool to 40~45 ℃, add preservative, stir until uniform, and the mixture is ready.

[0137] Application Example 2: Gentle and Skin-Nourishing Shower Gel

[0138] Table 5 Gentle and Skin-Nourishing Shower Gel Formula

[0139]

[0140] Preparation method:

[0141] Step 1: Mix and stir component A, then heat to 80~85 ℃ to obtain mixture I;

[0142] Step 2: Add component B to mixture I sequentially and stir until homogeneous to obtain mixture II;

[0143] Step 3: Cool mixture II to 40~45 ℃, add preservative, and stir until uniform.

[0144] Application Example 3: Cleansing Honey

[0145] Table 6 Refreshing Cleansing Honey Formula

[0146]

[0147] Step 1: Add water and potassium cocoyl glycinate from component A to a kettle, mix and stir, add hydroxypropyl methylcellulose and glycerol after premixing, stir until uniform, heat to 80~85 ℃ to obtain mixture I;

[0148] Step 2: Add component B to mixture I sequentially and stir until homogeneous to obtain mixture II;

[0149] Step 3: Cool mixture II to 40~45 ℃, add the (daily use) fragrance and PEG-40 hydrogenated castor oil after pre-dissolving, stir until uniform, then add the preservative and stir until uniform to obtain the final product.

[0150] Application Example 4: Gentle and Soothing Shower Gel

[0151] Table 7. Formula of Gentle and Soothing Body Wash

[0152]

[0153] Preparation method:

[0154] Step 1: Mix and stir component A, then heat to 80~85 ℃ to obtain mixture I;

[0155] Step 2: Add component B to mixture I sequentially and stir until homogeneous to obtain mixture II;

[0156] Step 3: Cool mixture II to 60-65 ℃, add component C, and obtain mixture III;

[0157] Step 4: Cool mixture III to 40~45 ℃ and add component D sequentially, stirring until homogeneous to obtain the final product.

[0158] Test Example 4: Viscosity Test

[0159] 1. Test method:

[0160] Application Examples 1, 2, 3, and 4 were measured, and their viscosities were compared with those of Application Examples 1, 2, 3, and 4. The Comparative Application Examples 1 to 4 were prepared by replacing Example 2 in Application Examples 1 to 4 with alkyl glucoside (APG), while keeping the other conditions and steps unchanged.

[0161] Among them, the viscosity measurement method is as follows:

[0162] Pour 200 g of sample into a 250 mL beaker and let it stand until no more bubbles appear. Adjust the sample temperature to within the range of (25±1) ℃ and record the measured temperature.

[0163] Using the appropriate rotor and rotational speed, test the viscosity of the sample at (25±1)℃. During the test, take care to avoid the formation of air bubbles, as this may affect the accuracy of the measurement results.

[0164] The instrument displays a stable reading, the original record is taken as an integer, and the final result is the average of three parallel tests.

[0165] 2. Test Results:

[0166] The experimental results are shown in Table 8.

[0167] Table 8 Viscosity Test Results

[0168] sample Viscosity Application Example 1 5025 Application Example 2 4691 Application Example 3 5318 Application Example 4 4866 Comparative Application Example 1 3429 Comparative Application Example 2 2582 Comparative Application Example 3 3644 Comparative Application Example 4 2907

[0169] As shown in Table 8, compared with the formulation with added APG, the formulation with modified APG prepared in this invention has a higher viscosity, indicating that the thickening properties of APG can be improved through modification.

[0170] 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. A method for preparing an alkyl glycoside sulfonate, characterized in that, Includes the following steps: Step S1: Add the alkyl glucoside solution to the reaction vessel, stir at 200-400 rpm and heat to 75-85 °C; wherein, the alkyl glucoside is one or more of octyl glucoside, decyl glucoside, lauryl glucoside, myristyl glucoside, and cocoyl glucoside, and the mass ratio of alkyl glucoside to water in the alkyl glucoside solution is 50:50; Step S2: Add the solid superbase to the reaction vessel from step S1, and react for 1-2 hours at a stirring speed of 400-600 rpm and a temperature of 85-90 ℃. After the reaction is complete, separate the solid superbase. The solid superbase is one of HND-61, HND-62, HND-63, and HND-64, and the mass ratio of the solid superbase to the alkyl glucoside is 1:(10-30). Step S3: Add 1,3-dichloro-2-propanol to the reaction vessel from step S2, and react for 6-8 h at a stirring speed of 100-200 rpm and a temperature of 90-95 ℃. Monitor the conversion rate and stop the reaction when the required conversion rate is reached. The molar ratio of 1,3-dichloro-2-propanol to the alkyl glucoside is (0.4-0.6):

1. Step S4: Add sodium 3-chloro-2-hydroxypropanesulfonate to the reaction vessel in step S3, and react for 6-8 h at a stirring speed of 200-400 rpm and a temperature of 80-85 ℃. Monitor the conversion rate, and stop the reaction when the requirement is met. Cool to 15-20 ℃, let stand for 48-72 h, and filter to obtain the product. The molar ratio of sodium 3-chloro-2-hydroxypropanesulfonate to the alkyl glucoside is (1-1.5):

1.

2. The method for preparing alkyl glycoside sulfonate according to claim 1, characterized in that, In step S2, the method of separating solid superalkali includes one or more of centrifugation, filtration, vacuum filtration, and pressure filtration.

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