An alkylglucoside derivative and a process for its preparation

Abstract

The application 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 application is prepared by chemically modifying the activity of a hydroxyl group on a glucoside sugar unit, specifically by first cross-linking through a cross-linking agent and then introducing an anionic sulfonic acid group. The alkyl glucoside derivative modified by sulfonation in the application has a significantly increased molecular weight, can not only reduce the transdermal penetration rate and the residual amount of a surfactant on the skin, but also help to form larger micelles, reduce the irritability of the surfactant to the skin, has higher mildness, and is suitable for formulating products with higher mildness requirements. In addition, the preparation method of the alkyl glucoside derivative provided by the application also has the advantages of high yield (the yield is more than 93%), simple operation, and high repeatability, and is conducive to the popularization and application of the alkyl glucoside derivative preparation process.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of daily chemicals, and particularly relates to an alkyl glucoside derivative and a preparation method thereof. BACKGROUND

[0002] Alkyl glucoside (alkyl glycoside, APG for short) is a kind of non-ionic surfactant formed by condensation reaction of sugar group (glucose) and fatty alcohol. With the enhancement of environmental awareness, the pollution problem of traditional synthetic surfactants is increasingly prominent. APG is rapidly popularized in the fields of washing, cosmetics, food and the like due to its natural source, biodegradability and low toxicity. APG has many advantages in the application process: (1) environmental protection, APG can be quickly degraded in the environment, reducing pollution and meeting the demand for sustainable development; (2) mildness, APG has low skin irritation and is suitable for personal care products (such as shampoo, skin care products); (3) multifunctionality, APG has emulsifying, dispersing, antibacterial and other properties, and is widely used in detergents, food additives (such as dairy stabilizers), agricultural biological pesticides and pharmaceutical fields (such as antiviral adjuvants); (4) stability, APG has high stability in a wide range of pH and temperature.

[0003] Although APG has obvious advantages, there are certain defects in APG based on different application scenarios and requirements, for example: relatively high cost, complex synthesis process, insufficient stability of some APG under extreme conditions such as high salt and high temperature, and narrow antibacterial spectrum, which needs to be compounded with other ingredients to enhance the effect. Taking the application of APG in personal cleaning products as an example, the main shortcomings of its application are: the relatively strong permeability, strong deproteinization and delipidation capacity, and large adsorption amount in the skin keratin layer caused by the non-ionic structure, which leads to certain damage to the skin barrier, false slip feeling after cleaning, heavy dry feeling of the skin after water dry, especially poor experience in autumn and winter.

[0004] In order to improve the performance of APG, the APG derivatives prepared by changing the length of alkyl chain, the type of sugar group or introducing functional groups can improve the defects of APG to different degrees. These derivatives can be applied to different scenes, greatly improving the application value of APG. At present, the synthesis method of APG derivatives still faces many problems, mainly in the low conversion rate of APG derivatives, poor regioselectivity of synthesis reaction, which leads to the difficulty in separation of the generated mixture product or high separation cost, seriously restricting the industrialized large-scale production of APG derivatives. SUMMARY

[0005] In order to solve the defects of the prior art, the present application provides an alkyl glucoside derivative with high yield, low production cost and good surface chemical performance and a preparation method thereof. The alkyl glucoside derivative provided by the present application is a chemical modification of the activity of the hydroxyl group on the glucose unit of glucoside. The alkyl glucoside derivative modified by sulfonation has a significantly larger molecular weight, can not only reduce the transdermal penetration rate, but also can reduce the residual amount of surfactants on the skin, and at the same time, can help to form larger micelles, reduce the irritation of surfactants to the skin, and has high mildness.

[0006] The technical scheme of the present application is as follows:

[0007] The present application provides an alkyl glucoside derivative, which is shown as formula I:

[0008] Formula I;

[0009] In the formula, R1 is or ; R2 is or H; or the same as R1;

[0010] x = 1-4;

[0011] y = 1-10, which represents the polymerization degree of EO;

[0012] z = 1-3, which represents the polymerization degree of APG molecule;

[0013] R is a C8-C 20 alkyl group, preferably a C8-C 10 alkyl group, a C8-C 14 alkyl group, a C8-C 16 alkyl group, a C8-C 18 alkyl group, a C 10 -C 12 alkyl group, a C 10 -C 14 alkyl group, a C 10 -C 16 alkyl group, a C 10 -C 18 alkyl group, a C 12 -C 14 alkyl group, a C 12 -C 16 alkyl group, a C 12 -C 18 alkyl group, a C 12 -C 20 alkyl group, an octyl (C8), a decyl (C 10 ), a lauryl (C 12 ), or a myristyl (C 14 ).

[0014] Further, in the alkyl glucoside derivative, when x = 1, R2 is H; R1 is wherein z = 1 ~ 3, R is C8-C 20 alkyl group, the C8-C 20 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 (C 10 ), lauryl (C 12 ), myristyl (C 14 ).

[0015] Further, in the alkyl glucoside derivative, when x = 2 ~ 4, R1 = R2, specifically wherein y = 1 ~ 10, z = 1 ~ 3, R is C8-C 20 alkyl group, the C8-C 20 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 20alkyl, octyl (C8), decyl (C10), lauryl (C12), myristyl (C14). 10 12 14

[0016] In addition, the application further provides a preparation method of the alkyl glucoside derivative, comprising the following steps:

[0017] Step S1, adding the alkyl glucoside solution and the solvent into a reaction container, and heating to 75-85 ℃ under the condition of 200-400 rpm, and stirring for 30-60 min;

[0018] Step S2, adding the activating agent into the reaction container in step S1 to react, and heating to 85-90 ℃ under the condition of 400-600 rpm, and reacting for 1-2 h;

[0019] Step S3, adding the crosslinking agent into the reaction container in step S2 to react, and monitoring the conversion rate, and stopping the reaction after the requirement is reached;

[0020] Step S4, adding the sulfonating agent into the reaction container in step S3 to react, and monitoring the conversion rate, and stopping the reaction after the requirement is reached, and cooling to 15-20 ℃, and standing for 12-24 h, and filtering, and taking the filtrate, and drying under reduced pressure to remove the solvent, and obtaining the alkyl glucoside derivative.

[0021] Further, the alkyl glucoside in step S1 is one or two or more of C 12 -C 16 alkyl glucoside, C 12 -C 18 alkyl glucoside, C 12 -C 20 alkyl glucoside, C8-C 14 alkyl glucoside, octyl glucoside, decyl glucoside, octyl / decyl glucoside, lauryl glucoside, myristyl glucoside, and coco glucoside; and the mass ratio of the alkyl glucoside solution to the solvent is (1.5-5):1.

[0022] Further, 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%; and the alkyl glucoside solution of the application is the alkyl glucoside with an active content of 50%.

[0023] Further, the solvent in step S1 is at least one of water, methanol, ethanol, isopropanol, acetone, and tetrahydrofuran; or is at least one of a mixture of water and methanol, water and ethanol, water and isopropanol, water and acetone, and water and tetrahydrofuran; and if the mixture of water and the organic solvent is selected, the volume ratio is (1-2):1. ​​​

[0024] Further, 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).

[0025] Further, the solid superbase catalyst can be obtained by commercial channels, such as HND-61, HND-62, HND-63, and HND-64, which are potassium carbonate supported on active alumina and obtained by sintering.

[0026] In the present application, if a water-soluble activator is selected, it can be directly used for the next reaction without treatment; if a solid superbase catalyst is selected, solid-liquid separation should be performed after the reaction, and the liquid is collected for the next reaction. The separation includes but is not limited to centrifugation, filtration, suction filtration, pressure filtration, and the like; and 200-mesh filter screen is preferred.

[0027] Further, the crosslinking agent in step S3 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, and the temperature is raised to 90-95°C at a speed of 100-200 rpm, and the reaction is performed for 6-8 h.

[0028] Further, the conversion rate of the crosslinking agent is monitored by HPLC, and the residual amount is ≤0.1 ppm (detection concentration 0.005 ppm, minimum quantitative concentration 0.025 ppm).

[0029] Further, the structure of the multi-arm polyethylene glycol chloride is as follows:

[0030] wherein m=2-6; n=1-3; molecular weight 0.4-2 K; for example: 6-ArmPEG-Cl (four-arm-polyethylene glycol-chloride), 8-ArmPEG-Cl (six-arm-polyethylene glycol-chloride), and the like.

[0031] Further, the sulfonating agent in step S4 is one of 2-chloroethylsulfonic acid sodium, 3-chloro-2-hydroxypropanesulfonic acid sodium, and 4-chloro-1-hydroxy-butanesulfonic acid sodium, and the molar ratio of the sulfonating agent to the alkyl glucoside is (1.2-2.0):1, and the temperature is raised to 80-85°C at a speed of 200-400 rpm, and the reaction is performed for 3-5 h.

[0032] Further, 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%).

[0033] Further, the filtration in the S4 step is mainly used to separate the particles precipitated during the standing process, and is preferably filtered with a 200-mesh filter screen; and the reduced-pressure drying can be selected from, but is not limited to, vacuum drying, freeze drying, etc., and the purpose is to remove the contained solvent.

[0034] The alkyl glucoside derivative prepared in the present application has a solid content of ≥96%, and the content of alkyl polyglucoside sulfonate derivative is ≥86%, the content of non-ionic substance is ≤10%, the content of inorganic salt is ≤4.0%, the residual amount of crosslinking agent is lower than the detection limit, and the residual amount of sulfonating agent is lower than the detection limit, as analyzed by HPLC. The obtained alkyl glucoside derivative can also be diluted with water, such as 60% solid content, 50% solid content, and 40% solid content, to be suitable for different application scenarios.

[0035] The alkyl glucoside derivative provided by the present application is prepared by chemically modifying the activity of the hydroxyl group on the glucoside sugar unit, specifically by crosslinking with a crosslinking agent and then introducing an anionic sulfonic acid group. The alkyl glucoside derivative modified by sulfonation in the present application has a significantly larger molecular weight, which can not only reduce the transdermal penetration rate, but also reduce the residual amount of surfactant on the skin, and at the same time help to form larger micelles, reduce the irritability of surfactants to the skin, have higher mildness, and be suitable for formulating products with higher mildness requirements, such as baby products, cleansing products, etc.

[0036] Meanwhile, the preparation method of the alkyl glucoside derivative provided by the present application also has the advantages of high yield, a yield of more than 93%, simple operation, and high repeatability, which is conducive to the popularization and application of the production process of the alkyl glucoside derivative.

[0037] In summary, compared with the prior art, the alkyl glucoside derivative provided by the present application has the following advantages:

[0038] (1) The alkyl glucoside derivative provided by the present application has the advantages of high mildness, low irritability, low residual amount, and easy cleaning, which can effectively solve the defects of strong deproteinization / fat removal ability, high irritability, and large residual amount of alkyl glucoside in personal cleaning products, and can effectively expand the application of alkyl glucoside.

[0039] (2) The production process of the alkyl glucoside derivative provided by the present application has the advantages of high yield, a yield of more than 93%, simple operation, and high repeatability, which is conducive to the large-scale popularization and application of the production process. DETAILED DESCRIPTION

[0040] The application is further described below by way of specific embodiments, but this is not a limitation of the application, and those skilled in the art can make various modifications or improvements according to the basic idea of the application, as long as they do not deviate from the basic idea of the application, and they are within the scope of the application. The materials and reagents involved in the application can be obtained by market or conventional technical means in the art.

[0041] Example 1, C 12 -C 16 Preparation of alkyl glucoside derivatives

[0042] Step S1, 696 g C 12 -C 16 The alkyl glucoside solution (1.0 mol, based on C 12 -C 16 The molecular formula of the alkyl glucoside is: C 18 H 36 O6, Mn = 348 g / mol), the C 12 -C 16 The alkyl glucoside solution is C 12 -C 16 The mixture of alkyl glucoside and water is C 12 -C 16 The mass ratio of alkyl glucoside and 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 container, and the temperature is raised to 75 ℃ under the condition of 200 rpm, and stirred for 30 min until the mixture is uniform;

[0043] Step S2, 34.8 g of sodium hydroxide (the mass ratio of sodium hydroxide to C 12 -C 16 The mass ratio of the alkyl glucoside solution is 1:20) is added to the reaction container in step S1 for reaction, and the temperature is raised to 85 ℃ under the condition of 400 rpm for 1 h;

[0044] Step S3, 100 g of four-arm-polyethylene glycol-chloride (4-ArmPEG-Cl, 0.25 mol, Mn = 400 g / mol) is added to the reaction container in step S2, and the temperature is raised to 90 ℃ under the condition of 100 rpm for 6 h, and the conversion rate of the crosslinking agent is monitored to a residual amount of 0.1 ppm, and the reaction is stopped after reaching the requirement;

[0045] Step S4, 252.9 g of sodium 2-chloroethyl sulfonate (1.5 mol, the molecular formula is: , Mn = 168.6 g / mol) into the reaction vessel in step S3, and the temperature was raised to 80 °C under the condition of 200 rpm for 3 h of reaction, and the conversion rate of sulfonating agent was monitored until the residual amount was not detected, and the reaction was stopped after reaching the requirement, and the temperature was cooled to 15 °C, and the reaction was placed for 12 h, and filtered with a 200 mesh filter screen, and C 12 -C 16 The alkyl glucoside derivative solution was vacuum dried to obtain C 12 -C 16 The alkyl glucoside derivative (721.5 g).

[0046] It was detected that the solid content was 96%, and the C 12 -C 16 The alkyl glucoside derivative content was 86%, the non-ionic substance was 10%, the inorganic salt was 4.0%, the crosslinking agent residual amount was not detected, the sulfonating agent residual amount was not detected, and the reaction yield of the present example was calculated to be 93.41%.

[0047] Example 2, preparation of lauryl glucoside derivative

[0048] Step S1, 696 g lauryl glucoside solution (1.0 mol, calculated based on lauryl glucoside, molecular formula: C 18 H 36 O6, Mn = 348 g / mol) was added to the reaction vessel, and the temperature was raised to 80 °C under the condition of 300 rpm for 45 min of stirring until the mixture was uniform, and 261 g water / ethanol (V:V = 2:1) mixed solvent (the mass ratio of water / methanol mixed solvent to lauryl glucoside solution was 1:2.67) was added to the reaction vessel, and the temperature was raised to 80 °C under the condition of 300 rpm for 45 min of stirring until the mixture was uniform;

[0049] Step S2, 34.8 g sodium carbonate (the mass ratio of sodium carbonate to lauryl glucoside solution was 1:20) was added to the reaction vessel in step S1 for reaction, and the temperature was raised to 90 °C under the condition of 500 rpm for 1.5 h of reaction;

[0050] Step S3, 167 g six-arm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.167 mol, Mn = 1000 g / mol) was added to the reaction vessel in step S2, and the temperature was raised to 92 °C under the condition of 150 rpm for 7 h of reaction, and the conversion rate of crosslinking agent was monitored until the residual amount was not detected, and the reaction was stopped after reaching the requirement;

[0051] Step S4, 297.9 g 3-chloro-2-hydroxypropanesulfonic acid sodium (1.5 mol, molecular formula: , Mn = 196.59 g / mol) into the reaction vessel in step S3, and heated to 82 ℃ at 300 rpm for 4 h, and the conversion rate of the sulfonating agent was monitored until the residual amount was not detected. After the reaction reached the requirement, the reaction was stopped, and the temperature was cooled to 16 ℃. After standing for 15 h, the lauryl glucoside derivative solution was filtered with a 200-mesh filter screen, and vacuum dried to obtain the lauryl glucoside derivative (825.7 g).

[0052] It was detected that the solid content was 98%, the lauryl glucoside derivative content was 90% by HPLC analysis, the non-ionic substance content was 8%, the inorganic salt content was 3.5%, the crosslinking agent residual amount was not detected, and the sulfonating agent residual amount was not detected. It was calculated that the reaction yield of the present example was 98.84%.

[0053] Example 3, C8-C 14 Preparation of alkyl glucoside derivative

[0054] Step S1, 640 g of C8-C 14 alkyl glucoside solution (1.0 mol, based on C8-C 14 alkyl glucoside, the molecular formula is: C 16 H 32 O6, Mn = 320 g / mol), the C8-C 14 alkyl glucoside solution is C8-C 14 alkyl glucoside and water, the mass ratio of C8-C 14 alkyl glucoside and water is 50:50, the free fatty alcohol content is <1.0%, and the free glucose content is <0.5%; 256 g of water / isopropyl alcohol (V:V = 1.5:1) mixed solvent (water / methanol mixed solvent and C8-C 14 alkyl glucoside solution at a mass ratio of 1:2.5) was added to the reaction vessel, and heated to 85 ℃ at 250 rpm for 60 min until the mixture was uniform;

[0055] Step S2, 32 g of solid superbase HND-61 (HND-61 and C8-C 14 alkyl glucoside solution at a mass ratio of 1:20) was added to the reaction vessel in step S1 for reaction, and heated to 86 ℃ at 600 rpm for 2 h. After the reaction was completed, the solid particles were filtered out with a 200-mesh filter screen;

[0056] Step S3, 167 g of six-arm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.167 mol, Mn = 1000 g / mol) was added to the reaction vessel in step S2, and heated to 95 ℃ at 200 rpm for 8 h. The conversion rate of the crosslinking agent was monitored until the residual amount was not detected. After the reaction reached the requirement, the reaction was stopped.

[0057] Step S4, 315.9 g of sodium 4-chloro-1-hydroxy-butane sulfonate (1.5 mol, Mn = 210.61 g / mol) was added into the reaction vessel in step S3, and the temperature was raised to 85 °C at 250 rpm for 5 h, and the sulfonating agent conversion was monitored to a residual amount of 0.1%, and the reaction was stopped after reaching the requirement, and cooled to 20 °C, and stood for 20 h, and filtered with a 200 mesh filter screen, and C8-C 14 The alkyl glucoside derivative solution was freeze-dried to obtain C8-C 14 The alkyl glucoside derivative (784.6 g).

[0058] The solid content was detected to be 97%, and the C8-C 14 The alkyl glucoside derivative content was 88%, the non-ionic content was 9%, the inorganic salt content was 3.7%, the crosslinking agent residual amount was not detected, the sulfonating agent residual amount was not detected, and the reaction yield of the present example was calculated to be 95.02%.

[0059] Example 4, preparation of octyl / decyl glucoside derivative

[0060] Step S1, 814 g of octyl / decyl glucoside solution (1.0 mol, calculated based on octyl / decyl glucoside, molecular formula: C 22 H 46 O6, Mn = 407 g / mol) was added into the reaction vessel, and the temperature was raised to 75 °C at 400 rpm for 35 min to mix uniformly, and 271.3 g of isopropyl alcohol (mass ratio of isopropyl alcohol to octyl / decyl glucoside solution was 1:3) was added into the reaction vessel, and the temperature was raised to 75 °C at 400 rpm for 35 min to mix uniformly;

[0061] Step S2, 32.56 g of sodium methoxide (mass ratio of sodium methoxide to octyl / decyl glucoside solution was 1:25) was added into the reaction vessel in step S1 for reaction, and the temperature was raised to 88 °C at 450 rpm for 1.5 h;

[0062] Step S3, 250 g of eight-arm-polyethylene glycol-chloride (8-Arm PEG-Cl, 0.125 mol, Mn = 2000 g / mol) was added into the reaction vessel in step S2, and the temperature was raised to 91 °C at 120 rpm for 6.5 h, and the crosslinking agent conversion was monitored to a residual amount of not detected, and the reaction was stopped after reaching the requirement;

[0063] Step S4, 297.9 g of 3-chloro-2-hydroxypropane sulfonic acid sodium salt (1.5 mol, molecular formula: C3H6ClNaO4S, Mn=196.59 g / mol) was added into the reaction vessel in step S3, and the temperature was raised to 81 ℃ at 400 rpm for 3.5 h, and the sulfonating agent conversion was monitored to a residual amount of 0.01 ppm, and the reaction was stopped after reaching the requirement, and cooled to 18 ℃, and stood for 24 h, and filtered with a 200 mesh filter screen, and the octyl / decyl glucoside derivative solution was taken, and freeze-dried to obtain the octyl / decyl glucoside derivative (906.8 g).

[0064] It was detected that the solid content was 96.5%, the octyl / decyl glucoside derivative content was 87% by HPLC analysis, the non-ionic substance was 7%, the inorganic salt was 3.8%, the crosslinking agent residual amount was not detected, the sulfonating agent residual amount was not detected, and the reaction yield of the present example was calculated to be 96.78%.

[0065] Example 5, preparation of cocoyl glucoside derivative

[0066] Step S1, 696 g of cocoyl glucoside solution (1.0 mol, calculated based on cocoyl glucoside, English name: COCO-GLUCOSIDE, molecular formula: C 18 H 36 O6, Mn=348 g / mol) was added into the reaction vessel, and the temperature was raised to 80 ℃ at 350 rpm for 45 min to mix uniformly, and 348 g of water (water to cocoyl glucoside solution mass ratio of 1:2) was added into the reaction vessel, and the temperature was raised to 80 ℃ at 350 rpm for 45 min to mix uniformly;

[0067] Step S2, 39.77 g of sodium hydroxide (sodium hydroxide to cocoyl glucoside solution mass ratio of 1:17.5) was added into the reaction vessel in step S1 for reaction, and the temperature was raised to 85 ℃ at 550 rpm for 1.2 h;

[0068] Step S3, 167 g of 6-arm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) was added into the reaction vessel in step S2, and the temperature was raised to 94 ℃ at 160 rpm for 7 h, and the crosslinking agent conversion was monitored to a residual amount of 0.05 ppm, and the reaction was stopped after reaching the requirement;

[0069] Step S4, 315.9 g of 4-chloro-1-hydroxy-butane sulfonic acid sodium salt (1.5 mol, Mn=210.61 g / mol) was added into the reaction vessel in step S3, and the temperature was raised to 84 ℃ at 350 rpm for 4 h, and the sulfonating agent conversion was monitored until the residual amount was not detected, and the reaction was stopped after reaching the requirement, and cooled to 19 ℃, and stood for 18 h, and filtered with a 200 mesh filter screen, and the cocoglycoside derivative solution was taken, and vacuum dried to obtain the cocoglycoside derivative (781.5 g).

[0070] It was detected that the solid content was 97%, the cocoglycoside derivative content was 88% by HPLC analysis, the non-ionic substance was 8.5%, the inorganic salt was 3.6%, the crosslinking agent residual amount was not detected, and the sulfonating agent residual amount was not detected, and the reaction yield of the present example was calculated to be 97.63%.

[0071] Example 6, preparation of lauryl glycoside derivative

[0072] Step S1, 696 g of lauryl glycoside solution (1.0 mol, calculated based on lauryl glycoside, molecular formula: C 18 H 36 O6, Mn=348 g / mol) was added into the reaction vessel, and the temperature was raised to 77 ℃ at 280 rpm for 40 min to mix uniformly, and 185.6 g of water (water to lauryl glycoside solution mass ratio was 1:3.75) was added into the reaction vessel, and the temperature was raised to 77 ℃ at 280 rpm for 40 min to mix uniformly;

[0073] Step S2, 34.03 g of solid superbase HND-63 (HND-63 to lauryl glycoside solution mass ratio was 1:20.45) was added into the reaction vessel in step S1 for reaction, and the temperature was raised to 90 ℃ at 400 rpm for 2 h, and after the reaction was completed, the solid particles were filtered out with a 200 mesh filter screen;

[0074] Step S3, 62.6 g of 1,3-dichloro-2-propanol (0.5 mol, molecular formula: C3H6Cl2O, Mn=128.98 g / mol) was added into the reaction vessel in step S2, and the temperature was raised to 93 ℃ at 180 rpm for 7.5 h, and the crosslinking agent conversion was monitored until the residual amount was not detected, and the reaction was stopped after reaching the requirement;

[0075] Step S4, 297.9 g of 3-chloro-2-hydroxypropane sulfonic acid sodium salt (1.5 mol, molecular formula: C3H6ClNaO4S, Mn=196.59 g / mol) was added into the reaction vessel in step S3, and the temperature was raised to 80°C at 280 rpm for 4.5 h, and the sulfonating agent conversion was monitored until the residual amount was not detected, and the reaction was stopped after reaching the requirement, and cooled to 17°C, and stood for 16 h, and filtered with a 200 mesh filter screen, and the lauryl glucoside solution was taken, and freeze-dried to obtain the lauryl glucoside derivative (622.8 g).

[0076] It was detected that the solid content was 96%, the lauryl glucoside derivative content was 86% by HPLC analysis, the non-ionic substance was 10%, the inorganic salt was 4.0%, the crosslinking agent residual amount was not detected, and the sulfonating agent residual amount was not detected, and the reaction yield of the present example was calculated to be 95.39%.

[0077] Comparative Example 1, preparation of lauryl glucoside sulfonate derivative

[0078] The difference from Example 2 is that no sodium carbonate activator is added in step S2, and water is supplemented, and the other steps are similar to Example 2.

[0079] The results show that the reaction can be normal, the final product lauryl glucoside sulfonate derivative system is turbid, the content is low, and the molecular weight is small.

[0080] Comparative Example 2, preparation of lauryl glucoside sulfonate derivative

[0081] The difference from Example 2 is that 167 g of 6-arm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) in step S3 is replaced by 167 g of water, and the other steps are similar to Example 2.

[0082] The results show that the reaction can be normal, and the molecular weight of the final product lauryl glucoside sulfonate derivative is small.

[0083] Comparative Example 3, preparation of lauryl glucoside sulfonate derivative

[0084] The difference from Example 2 is that 167 g of 6-arm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.167 mol, Mn=1000 g / mol) in step S3 is replaced by 42.8 g of 6-arm-polyethylene glycol-chloride (6-ArmPEG-Cl, 0.0428 mol, Mn=1000 g / mol) and 124.2 g of water, and the other steps are similar to Example 2.

[0085] The results show that the reaction can be normal, and the molecular weight of the final product lauryl glucoside sulfonate derivative is small.

[0086] Preparation of lauryl glucoside sulfonate derivative

[0087] The difference from Example 2 is that 167 g of 6-ArmPEG-Cl (0.167 mol, Mn = 1000 g / mol) in step S3 is replaced by 250 g of 6-ArmPEG-Cl (0.25 mol, Mn = 1000 g / mol), and other steps are similar to Example 2.

[0088] The results show that the reaction cannot proceed normally, a large amount of insoluble substance is generated, and the product is layered.

[0089] Preparation of lauryl glucoside sulfonate derivative

[0090] The difference from Example 2 is that 297.9 g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt (1.5 mol, Mn = 196.59 g / mol) in step S4 is replaced by 297.9 g of water, and other steps are similar to Example 2.

[0091] The results show that the reaction can proceed normally, but the lauryl glucoside sulfonate derivative cannot be obtained, a large amount of insoluble substance is generated, and the product is layered.

[0092] Preparation of lauryl glucoside sulfonate derivative

[0093] The difference from Example 2 is that 297.9 g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt (1.5 mol, Mn = 196.59 g / mol) in step S4 is replaced by 198.59 g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt (1.0 mol, Mn = 196.59 g / mol) and 99.31 g of water, and other steps are similar to Example 2.

[0094] The results show that the reaction can proceed normally, but the lauryl glucoside sulfonate derivative cannot be obtained, a large amount of insoluble substance is generated, and the product is layered.

[0095] Preparation of lauryl glucoside sulfonate derivative

[0096] The difference from Example 2 is that 297.9 g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt (1.5 mol, Mn = 196.59 g / mol) in step S4 is replaced by 595.77 g of 3-chloro-2-hydroxypropanesulfonic acid sodium salt (3.0 mol, Mn = 196.59 g / mol), and other steps are similar to Example 2.

[0097] The results show that normal reaction can be achieved, and more insoluble substances are generated, and the layers are separated.

[0098] Test Example 1: Physical and chemical index detection of alkyl glucoside derivatives

[0099] 1. Test method:

[0100] The physical and chemical indexes of the alkyl glucoside derivatives prepared in Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, Comparative Example 6 and Comparative Example 7 were detected.

[0101] 2. Test results:

[0102] The test results are shown in Table 1.

[0103] Table 1: Results of physical and chemical index detection

[0104] Sample State of material Solid content (%) Nonionic content (%) Active content (%) Inorganic salt content (%) Crosslinker residue (ppm) Sulfonating agent residue (%) Example 1 Uniform transparent viscous state 96 10 86 4.0 Not detected Not detected Example 2 Uniform transparent viscous state 98 8.0 90 3.5 Not detected Not detected Example 3 Uniform transparent viscous state 97 9.0 88 3.7 Not detected Not detected Example 4 Uniform transparent viscous state 96.5 7.0 87 3.8 Not detected Not detected Example 5 Uniform transparent viscous state 97 8.5 88 3.6 Not detected Not detected Example 6 Uniform transparent viscous state 98 8.0 90 3.0 Not detected Not detected Comparative Example 1 Turbid viscous state 98 35 55 2.4 1200 3.2 Comparative Example 2 Uniform transparent viscous state 96 15 77 3.5 / 0.69 Comparative Example 3 Uniform transparent viscous state 97 11 82 2.2 / Not detected Comparative Example 4 Turbid viscous state 95 30 62 3.7 6500 2.2 Comparative Example 5 Turbid viscous state 95 92 / 3.6 Not detected / Comparative Example 6 Uniform transparent viscous state 96 16 76 3.5 Not detected Not detected Comparative Example 7 Turbid viscous state 98 6.5 87 5.5 Not detected 1.3

[0105] As can be seen from Table 1, the alkyl glucoside sulfonate derivatives of Examples 1-6 of the present application can all be obtained, the conversion rate of sulfonate is high, and the final product is uniform and transparent. In Comparative Example 1, no activator is added, which can be seen to affect the subsequent crosslinking and sulfonation reactions, the conversion rate is low, and the final product is turbid due to precipitation; in Comparative Examples 2-4, the effects of not adding a crosslinking agent, adding an insufficient amount of a crosslinking agent and adding an excessive amount of a crosslinking agent are investigated, respectively, which can be seen to affect the sulfonation efficiency, resulting in high nonionic content and low sulfonate content, and excessive addition of a crosslinking agent can cause normal reaction to be impossible, more insoluble substances to be generated, and the layers to be separated; in Comparative Examples 5-7, the effects of not adding a sulfonating agent, adding an insufficient amount of a sulfonating agent and adding an excessive amount of a sulfonating agent are investigated, respectively, and the results show that no sulfonate derivative can be obtained without adding a sulfonating agent, the conversion rate is not enough with insufficient addition of a sulfonating agent, but excessive addition of a sulfonating agent can cause more insoluble substances to be generated in the system, the layers to be separated, the final product to be turbid, and the residual amount of the sulfonating agent to be large.

[0106] Test Example 2: Determination of molecular weight of alkyl glucoside derivatives

[0107] 1. Test method:

[0108] A gel permeation chromatograph (GPC, manufacturer: Waters Corporation, USA; model: Waters 1525 / 2414) was used to determine the molecular weight of the alkyl glucoside derivatives prepared in Example 1, Example 2, Example 3, Example 4, Example 5 and Example 6, a THF solution of chromatographic purity was selected as the mobile phase, the flow rate was 1.0 mL / min, the chromatographic column was calibrated with a monodisperse polystyrene standard, and the test temperature was 30 ℃. Lauryl glucoside was used as a control sample.

[0109] Test results:

[0110] The test results are shown in Table 2.

[0111] Table 2 Molecular weight determination results

[0112] 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

[0113] As the molecular weight increases beyond 500 daltons, the absorption of the molecules by normal human skin decreases rapidly. This means that large molecular weight surfactant molecules are not easily penetrated into the human skin, reducing the irritation of the surfactant.

[0114] As can be seen from Table 2, after the alkyl glucoside of the present application is modified by sulfonation, the molecular weight is significantly increased, which helps to reduce the transdermal penetration rate, and also helps to form larger micelles, reducing the irritation to the skin.

[0115] Test Example Three, Determination of Critical Micelle Concentration of Alkyl Glucoside Derivatives

[0116] 1. Test method:

[0117] Determination of the critical micelle concentration of the alkyl glucoside derivatives prepared in Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, Comparative Example 6 and Comparative Example 7.

[0118] Determination by fluorescence spectroscopy. Pyrene is a strong hydrophobic probe with very low solubility in water. When micelles and other macromolecular systems are present, pyrene preferentially dissolves in the internal hydrophobic region of these aggregates. The fluorescence emission spectrum of pyrene solution shows five characteristic peaks, and the relative intensity of the peaks is different in environments of different polarity. Among them, the ratio of the first characteristic peak 373 nm (I1) to the third characteristic peak 384 nm (I3) of the pyrene molecule (I1 / I3) is very sensitive to the polarity of the environment, and decreases with the decrease of the environmental polarity. Pyrene is solubilized in different concentrations of surfactant solution. When the concentration of surfactant is small, pyrene in the solution almost exists in the water phase, and the value of I1 / I3 is similar to that of pyrene in water. When the concentration of the solution is greater than the critical micelle concentration (CMC), micelles are formed, and pyrene will enter the internal hydrophobic region of the micelles from the water phase. The change of environmental polarity will cause a sudden change in the value of I1 / I3. By finding the mutation point in the curve of I1 / I3 and surfactant concentration, the critical micelle concentration (CMC) of the surfactant can be obtained. Take lauryl glucoside as the control sample. cmc cmc

[0119] 2. Test results

[0120] The test results are shown in Table 3.​​

[0121] Table 3 Critical micelle concentration (CMC) cmc Test results

[0122] 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

[0123] 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.

[0124] 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.

[0125] Experimental Example 4: Test of the micelle aggregation number of alkyl glucoside derivatives

[0126] 1. Test method:

[0127] 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.

[0128] 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.

[0129] 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 was set to an excitation wavelength of 335 nm and the fluorescence intensity was read at a wavelength of 373 nm. Assuming that the pyrene molecules and the benzophenone molecules follow a Poisson distribution between the micelles, Nm can be calculated by the following formula:

[0130] ;

[0131] wherein: I1, I0- fluorescence intensity of the sample at a wavelength of 373 nm with and without the quencher;

[0132] C Q - concentration of the fluorescence quencher;

[0133] S T - total concentration of the surfactant solution.

[0134] 2. Test results:

[0135] The test results are shown in Table 4.

[0136] Table 4 Nm (micelle aggregation number) test results

[0137] Sample Nm (micellar 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

[0138] The micelle aggregation number refers to the minimum number of molecules required for the formation of micelles when the surfactant molecules reach a certain concentration in the solution. The formation of micelles is an important characteristic of surfactants, which affects the performance of surfactants in various applications, such as washing, emulsification, dispersion, etc.

[0139] As can be seen from Table 4, compared with lauryl glucoside, the alkyl glucoside sulfonate derivatives prepared in Examples 1-6 of the present application have a larger micelle aggregation number, a larger micelle size, and are not easy to penetrate into the stratum corneum, which corresponds to their higher mildness.

[0140] Test Example Five: Safety test of alkyl glucoside derivatives

[0141] Test method:

[0142] Irritation test:

[0143] The irritation of the alkyl glucoside derivatives prepared in Example 1, Example 2, Example 3, Example 4, Example 5, Example 6, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, Comparative Example 5, Comparative Example 6 and Comparative Example 7 was determined by the zein method. Lauryl glucoside was used as a control sample.

[0144] 1.2. Toxicity performance test:

[0145] The alkyl glucoside derivative prepared in Example 2 was selected for the toxicity performance test.

[0146] 2. Test results:

[0147] The test results are shown in Tables 5 and 6.

[0148] 2.1. The irritation test results are shown in Table 5.

[0149] Table 5. Irritation test results

[0150] 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

[0151] Zein, which is almost completely insoluble in water, interacts with surfactants, and its water solubility increases. Strongly irritating surfactants are more likely to dissolve zein than weakly irritating surfactants. Therefore, the solubility of zein after interaction with surfactants is determined according to the change in nitrogen content in the aqueous solution before and after the interaction of the surfactants. The nitrogen content in the dissolved zein is directly proportional to the skin irritation caused by the surfactants, and thus the irritation of the surfactants can be understood.

[0152] As shown in Table 5, the alkyl glucoside sulfonate derivative prepared in Examples 1-6 of the present application has low irritation.

[0153] 2.2. The toxicity performance test results are shown in Table 6.

[0154] Table 6. Toxicity performance test results

[0155] No. Item Test result 1 Acute skin irritation test No irritation 2 Skin allergy test No skin allergy observed 3 Skin phototoxicity test No skin phototoxicity observed 4 Skin photoallergy test Sensitization rate: 0%, sensitization grade: I, sensitization intensity: weak 5 Bacterial reverse mutation test Negative 6 In vitro mammalian cell chromosome aberration test Negative 7 Acute percutaneous toxicity test LD 50 > 2500 mg / kg <!-- 12 -->]]> 8 28-day repeated dose percutaneous toxicity test NOAEL value: 1000 mg / kg BW / d

[0156] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present application and do not limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

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. The method for preparing the alkyl glucoside derivative according to any one of claims 1 to 3, 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. Stop the reaction when the required conversion rate is reached. Cool to 15-20 °C, let stand for 12-24 h, filter, take the filtrate, dry under reduced pressure to remove the solvent, and obtain the product. 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 hours. 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.

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, C8-C 14 One of the alkyl glucosides; 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, The structure of the multi-arm polyethylene glycol chloride is as follows: Where m=2~4; n=1~3; molecular weight 0.4~2 K.

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