Sugar-modified polyorganosiloxane emulsifier, and preparation method and application thereof

Abstract

This invention relates to a method for preparing organosilicon-modified glycosides and the application of sugar-modified polyorganosiloxane emulsifiers prepared using this product. The method for preparing organosilicon-modified glycosides first involves reacting a ketone compound with a sugar compound under an acid catalyst to obtain a reaction system containing a sugar intermediate. Then, a glycidyl ether compound containing a carbon-carbon double bond is added to the reaction system containing the sugar intermediate to obtain an alkyl glycoside. Finally, the alkyl glycoside is reacted with a hydrosiloxane to obtain the organosilicon-modified glycoside. This organosilicon-modified glycoside is dispersed in cyclodimethylsiloxane, polydimethylsiloxane, or isododecane to obtain the sugar-modified polyorganosiloxane emulsifier. This preparation method reduces the self-condensation of sugars during alkyl glycoside preparation by first protecting the hydroxyl groups on the sugar. Simultaneously, the use of a glycidyl ether compound containing an epoxy group to prepare the alkyl glycoside consumes the water generated during the preparation of the alkyl glycoside, promoting the normal progress of the reaction. The sugar-modified polyorganosiloxane emulsifier prepared by this invention exhibits good emulsification stability.

Description

Technical Field

[0001] This invention relates to the field of daily chemical products technology, and more specifically, to a sugar-modified polyorganosiloxane emulsifier, its preparation method, and its application. Background Technology

[0002] Alkyl glycosides possess the characteristics of both anionic and nonionic surfactants. They are composed of a relatively rigid hydrophilic sugar moiety and a relatively flexible alkyl chain moiety with controllable chain length, linked by glycosidic bonds. They are easily soluble in water, have low surface tension, high activity, strong detergency, and are non-toxic, non-irritating, and have good biodegradability. They can be widely used as surfactants, emulsifiers, and humectants in detergents, cosmetics, and food.

[0003] Alkyl glycosides can be stored for extended periods over a wide temperature range and also possess humectant properties, fully meeting the performance requirements of active ingredients in cosmetics. Alkyl glycosides have been used as active ingredients in cosmetics both domestically and internationally, and these new cosmetics exhibit excellent skin moisturizing and skin-care properties. Currently, some quality problems still exist in personal cleansers, the most serious being the presence of excessive levels of toxic substances such as mercury (Hg), phosphorus (Pb), and astaxanthin (As), which not only severely damage the skin and hair but also pollute the environment. The new generation of shampoos and bath liquids made with alkyl glycosides as a base have strong foaming power, producing white, fine foam that softens the skin, is non-irritating to the eyes, does not pollute the environment, has good hard water resistance, and possesses excellent conditioning and care functions.

[0004] In shampoos, alkyl glycosides are essential ingredients in low-irritant and children's shampoos because they are non-irritating to human skin and eyes and can reduce the irritation of other surfactants they are formulated with. The mildness of alkyl glycosides protects damaged hair and they can be used as surfactants in hair dyeing and perming. When combined with protein hydrolysates, their styling properties are comparable to commonly used styling agents such as polyvinylpyrrolidone, but they are easier to rinse. Alkyl glycosides can be used to formulate a new generation of shampoos and bath gels with strong foaming power and fine lather.

[0005] In hair conditioners, alkyl glycosides have a softening effect on the skin, are non-irritating to the eyes, and provide excellent conditioning and nourishing effects on the hair. Their synergistic effect with quaternary ammonium salts helps improve wet combability, while dry combability remains largely unchanged. Adding oils, such as octyldodecyl alcohol, to the conditioner will further improve wet combability.

[0006] The use of alkyl glycosides as emulsifiers in cosmetics can reduce the irritation of the formula, increase its moisturizing effect, and improve the efficacy of functional products.

[0007] Currently, most industrial glycoside preparations utilize indirect glycosylation. Under an acidic catalyst, glucose reacts with short-chain fatty alcohols to generate short-chain alkyl glycosides. These short-chain fatty alcohols are then replaced with long-chain fatty alcohols through a glycoside exchange reaction to obtain long-chain alkyl glycosides. This method requires no complex raw materials and is relatively low-cost. However, the reaction between glucose and fatty alcohols is a condensation reaction, which produces water. To avoid affecting the reaction process and efficiency, this water must be removed promptly. Water removal must be carried out under reduced pressure, increasing the difficulty of process control. Patent US5831080 describes an acidic catalytic method for alkyl glycoside preparation. Water is produced as a byproduct during this process, requiring post-treatment in subsequent steps, making the process relatively complex. Furthermore, glucose, being a polyhydroxy compound, also undergoes side reactions during alkyl glycoside preparation. Residual glucose in the glycoside can transform into other impurities, altering the glycoside's odor and color. According to the literature published by China Academic Journals Electronic Press (1006-7264(2009)06-0021-04), under acidic conditions, the hydroxyl groups within glucose molecules undergo condensation to form furfural derivatives. These furfural derivatives then undergo dehydration condensation under acidic conditions, turning black and forming a black, tarnished substance. Patent CN112979720B indicates that the prepared alkyl glycosides require decolorization, which is achieved using a decolorizing agent. CN106831899B similarly states that alkyl glycosides also require decolorization. Therefore, side reactions during the preparation of alkyl glycosides should be avoided and minimized as much as possible.

[0008] Another method for preparing sugar-modified polyoxygen organosiloxane emulsifiers involves reacting amino silicone oil and glycolactones under heating conditions. This requires adding alcohols or esters as solvents during the reaction to promote its progress. After the reaction is complete, the solvent and odor are removed under reduced pressure, and the final product collected is the sugar-modified polyoxygen organosiloxane. Summary of the Invention

[0009] The primary objective of this invention is to overcome the shortcomings and deficiencies of existing alkyl glycoside emulsifier preparation processes, such as complex dehydration processes and glucose self-condensation, and to provide a method for preparing organosilicon-modified glycosides.

[0010] A further object of the present invention is to provide a sugar-modified polyorganosiloxane emulsifier.

[0011] A further object of the present invention is to provide the application of the above-mentioned sugar-modified polyorganosiloxane emulsifier in daily chemical products.

[0012] The above-mentioned objective of the present invention is achieved through the following technical solution:

[0013] A method for preparing an organosilicon-modified glycoside includes the following steps:

[0014] S1 ketones react with hydroxyl groups on carbohydrates in the presence of an acid catalyst to produce an acetal reaction, yielding a reaction system containing carbohydrate intermediates; the carbohydrates are monosaccharides and / or disaccharides.

[0015] S2. Add a glycidyl ether compound containing a carbon-carbon double bond to the reaction system containing the carbohydrate intermediate obtained in step S1 and heat it to obtain an alkyl glycoside.

[0016] S3 involves an addition reaction between a hydrosiloxane and the alkyl glycoside obtained in step S2 to obtain an organosilicon-modified glycoside.

[0017] This invention employs an acetal reaction between ketone compounds and the hydroxyl groups on carbohydrate compounds to protect the hydroxyl groups and reduce self-condensation during the preparation of alkyl glycosides. Simultaneously, it utilizes glycidyl ether compounds containing carbon-carbon double bonds to react with carbohydrate compounds to prepare alkyl glycosides. These glycidyl ether compounds possess hydrolyzable epoxy groups; the hydrolysis of these epoxy groups produces hydroxyl groups, which react with the carbohydrate compounds to generate alkyl glycosides. The hydrolysis of these epoxy groups consumes the water generated during the alkyl glycoside reaction, promoting the normal progress of the reaction.

[0018] Preferably, the ketone compound in step S1 is one of acetone, butanone, pentanone, cyclohexanone, and phenylacetone.

[0019] Preferably, the carbohydrate compound in step S1 is one of glucose, fructose, sucrose, lactose, and maltose.

[0020] Preferably, the molar ratio of glucose to ketone compounds in step S1 is 1:4 to 4.5.

[0021] Preferably, the reaction temperature in step S1 is 50-60°C and the reaction time is 4-5 hours.

[0022] Preferably, the glycidyl ether compound containing a carbon-carbon double bond in step S2 is at least one of allyl glycidyl ether, vinylphenyl glycidyl ether, and o-diallyl bisphenol A diglycidyl ether.

[0023] Preferably, in step S2, the amount of glycidyl ether compound containing carbon-carbon double bonds added is based on the molar amount of water produced by the S1 acetal reaction theory, and the ratio of the number of moles of water produced by the S1 acetal reaction theory to the number of moles of epoxy groups in the glycidyl ether compound containing carbon-carbon double bonds is 1 to 1.3:1.

[0024] Preferably, the acid catalyst in step S1 is one of sulfuric acid, hydrochloric acid, trifluoromethanesulfonic acid, phosphoric acid, or acidic clay.

[0025] Preferably, the amount of acid catalyst added in step S1 is 0.5 to 1.5 wt% of the reaction system.

[0026] Preferably, the heating temperature in step S2 is 100–120°C.

[0027] Preferably, the heating reaction time in step S2 is 1 to 1.5 hours.

[0028] In this invention, step S2 is performed under normal pressure.

[0029] Preferably, in step S3, the hydrogen-containing siloxane is at least one of double-ended hydrogen-containing silicone oil, side-chain hydrogen-containing silicone oil, or single-ended hydrogen-containing silicone oil.

[0030] Preferably, in step S3, the molar ratio of the carbon-carbon double bond group of the alkyl glycoside to the hydrogen-containing group of the hydrogen-containing siloxane is 1:1.

[0031] A sugar-modified polyorganosiloxane emulsifier is obtained by dispersing the organosilicon-modified glycoside prepared by the above preparation method in cyclodimethylsiloxane, polydimethylsiloxane or isododecane.

[0032] Preferably, in the sugar-modified polyorganosiloxane emulsifier, the organosilicon-modified glycoside accounts for 17-22% by mass.

[0033] This invention also protects the application of the above-mentioned sugar-modified polyorganosiloxane emulsifier in daily chemical products.

[0034] Compared with the prior art, the beneficial effects of the present invention are:

[0035] (1) The method for preparing organosilicon modified glycosides of the present invention first protects the hydroxyl groups on the sugar compounds to reduce the self-condensation of the sugar compounds during the preparation of alkyl glycosides. At the same time, it uses glycidyl ether compounds containing epoxy groups to prepare alkyl glycosides with sugar compounds. The hydrolysis of epoxy groups can consume the water generated in the preparation of alkyl glycosides, simplifying the water removal process in the existing preparation of alkyl glycosides and promoting the normal progress of the reaction.

[0036] (2) The sugar-modified polyorganosiloxane emulsifier prepared by the present invention has excellent emulsification stability when applied to daily chemical product formulations. Attached Figure Description

[0037] Figure 1 The image shows the infrared spectrum of the glucose intermediate prepared in Example 1.

[0038] Figure 2 The infrared spectrum of the allyl glucoside prepared in Example 1 is shown. Detailed Implementation

[0039] To more clearly and completely describe the technical solution of the present invention, the present invention will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention. Various changes can be made within the scope of the claims of the present invention.

[0040] Example 1

[0041] This embodiment provides a method for preparing organosilicon-modified glycosides and sugar-modified polyorganosiloxane emulsifiers, the specific preparation steps of which are as follows:

[0042] S1 acetone reacts with glucose in an acetal reaction to obtain a reaction system containing a glucose intermediate.

[0043] Weigh 18g of glucose and 24g of acetone. After stirring for ten minutes, slowly add 0.21g of concentrated sulfuric acid. Heat the reaction to 50°C and let it react for 4 hours. Then stop heating the reaction. The result is a reaction system containing 34g of glucose intermediate (the reaction system contains 26g of glucose intermediate, 3.6g of water, 0.21g of concentrated sulfuric acid and excess acetone).

[0044] S2 is heated to react the reaction system containing glucose intermediate in step S1 with allyl glycidyl ether to obtain alkyl glucoside.

[0045] Weigh 22.8 g of allyl glycidyl ether and slowly add it to the reaction system of the above glucose intermediate. Heat the reaction to 110°C and react for 2 hours. Then add 0.63 g of sodium carbonate to neutralize the concentrated sulfuric acid. Filter the product to remove inorganic salts and other impurities, and collect the liquid as alkyl glucoside.

[0046] S3 involves an addition reaction between a hydrogen-containing siloxane and the alkyl glucoside obtained in step S2 to obtain an organosilicon-modified glucoside.

[0047] 18g of alkyl glucoside and 63.4g of hydrogen-containing silicone oil were weighed, and 0.14g of caster catalyst was added. The mixture was heated to 110℃ and reacted for 3 hours. After the reaction was completed, the mixture was subjected to vacuum devolatilization for 1 hour, and the liquid was collected, which is the organosilicon-modified glucoside.

[0048] S4. The organosilicon-modified glucosinolate obtained in step S3 is dispersed in decamethylcyclopentasiloxane to obtain emulsifier-1.

[0049] In step S1, the molar ratio of acetone to glucose is 4:1.

[0050] In step S2, the molar ratio of water produced by the acetal reaction in S1 to the epoxy group in the allyl glycidyl ether is 1.3:2.

[0051] In step S3, the molar ratio of the carbon-carbon double bond in the alkyl glucoside to the hydrogen-containing group in the hydrogen-containing siloxane is 1:1.

[0052] In step S4, the organosilicon-modified glucoside has a mass percentage of 20% in the emulsifier.

[0053] Example 2

[0054] S1 acetone reacts with glucose in an acetal reaction to obtain a reaction system containing a glucose intermediate.

[0055] Consistent with Example 1.

[0056] S2 Add vinylphenyl glycidyl ether to the reaction system containing glucose intermediate obtained in step S1 and heat it under the catalysis of an acid catalyst to obtain alkyl glucoside.

[0057] Weigh 35.2 g of vinylphenyl glycidyl ether and slowly add it to the glucose intermediate reaction system in step S1. Heat the reaction to 110°C and react for 2 hours. Then add 0.63 g of sodium carbonate to neutralize the concentrated sulfuric acid. Filter the product to remove inorganic salts and other impurities, and collect the liquid as alkyl glucoside.

[0058] S3 involves an addition reaction between a hydrogen-containing siloxane and the alkyl glucoside obtained in step S2 to obtain an organosilicon-modified glucoside.

[0059] 18g of alkyl glucoside and 52g of hydrogen-containing silicone oil were weighed, and 0.11g of caster catalyst was added. The mixture was heated to 110℃ and reacted for 3 hours. After the reaction was completed, the mixture was subjected to vacuum devolatilization for 1 hour, and the liquid was collected, which is the organosilicon-modified glucoside.

[0060] S4. The organosilicon-modified glucosinolate obtained in step S3 is dispersed in decamethylcyclopentasiloxane to obtain emulsifier-2.

[0061] The molar ratio of water to vinylphenyl glycidyl ether produced by the S1 acetal reaction is 1:2.

[0062] In step S4, the organosilicon-modified glucoside has a mass percentage of 20% in the emulsifier.

[0063] Example 3

[0064] S1 acetone reacts with glucose in an acetal reaction to obtain a reaction system containing a glucose intermediate.

[0065] Consistent with Example 1.

[0066] S2 weighed 42g of o-diallylbisphenol A diglycidyl ether and slowly added it to the above glucose intermediate reaction system. The reaction was heated to 110℃ and reacted for 2 hours. Then, 0.63g of sodium carbonate was added to neutralize the concentrated sulfuric acid. The product was filtered to remove inorganic salts and other impurities, and the collected liquid was the alkyl glucoside.

[0067] S3 involves an addition reaction between a hydrogen-containing siloxane and the alkyl glucoside obtained in step S2 to obtain an organosilicon-modified glucoside.

[0068] 18g of alkyl glucoside and 47.2g of hydrogen-containing silicone oil were weighed, and 0.11g of caster catalyst was added. The mixture was heated to 110℃ and reacted for 3 hours. After the reaction was completed, the mixture was subjected to vacuum devolatilization for 1 hour, and the liquid was collected, which is the organosilicon-modified glucoside.

[0069] S4. The organosilicon-modified glucosinolate obtained in step S3 is dispersed in decamethylcyclopentasiloxane to obtain emulsifier-3.

[0070] The molar ratio of water to o-diallyl bisphenol A diglycidyl ether produced by the S1 acetal reaction is 1:1.

[0071] In step S4, the organosilicon-modified glucoside has a mass percentage of 20% in the emulsifier.

[0072] Example 4

[0073] S1 acetone reacts with glucose in an acetal reaction to obtain a reaction system containing a glucose intermediate.

[0074] Consistent with Example 1.

[0075] S2. Allyl glycidyl ether is added to the reaction system containing glucose intermediate obtained in step S1 and heated under acid catalyst to obtain alkyl glucoside.

[0076] Weigh 22.8 g of allyl glycidyl ether and slowly add it to 34 g of glucose intermediate. Heat the reaction mixture to 110 °C and react for 3 hours. Then, add 0.63 g of sodium carbonate to neutralize the concentrated sulfuric acid. Filter the product to remove inorganic salts and other impurities, and collect the liquid as alkyl glucoside.

[0077] S3 involves an addition reaction between a hydrogen-containing siloxane and the alkyl glucoside obtained in step S2 to obtain an organosilicon-modified glucoside.

[0078] 18g of alkyl glucoside and 63.4g of hydrogen-containing silicone oil were weighed, and 0.14g of caster catalyst was added. The mixture was heated to 110℃ and reacted for 3 hours. After the reaction was completed, the mixture was subjected to vacuum devolatilization for 1 hour, and the liquid was collected, which is the organosilicon-modified glucoside.

[0079] S4 Disperse the organosilicon-modified glucosinolate obtained in step S3 in decamethylcyclopentasiloxane to obtain emulsifier-4;

[0080] In step S4, the organosilicon-modified glucoside has a mass percentage of 20% in the emulsifier.

[0081] Comparative Example 1

[0082] This comparative example provides a method for preparing organosilicon-modified glucosinolates and sugar-modified polyoxygen organosilicon emulsifiers, the preparation process of which is as follows:

[0083] S1 involves reacting glucose with allyl glycidyl ether under an acid catalyst with heating to obtain alkyl glucoside.

[0084] Weigh 18g of glucose, add 22.8g of allyl glycidyl ether, and slowly add 0.2g of concentrated sulfuric acid. Heat the reaction to 110℃ and react for 3 hours. Then add 0.63g of sodium carbonate to neutralize the concentrated sulfuric acid. Filter the product to remove inorganic salts and other impurities, and collect the liquid as alkyl glucoside.

[0085] S3 involves an addition reaction between a hydrogen-containing siloxane and the alkyl glucoside obtained in step S2 to obtain an organosilicon-modified glucoside.

[0086] 18g of alkyl glucoside and 88.2g of hydrosilicone oil were weighed, and 0.17g of caster catalyst was added. The mixture was heated to 110℃ and reacted for 3 hours. After the reaction was completed, the mixture was subjected to vacuum devolatilization for 1 hour, and the liquid was collected, which is the organosilicon-modified glucoside.

[0087] S4. The organosilicon-modified glucosinolate obtained in step S3 is dispersed in decamethylcyclopentasiloxane to obtain the emulsifier. The emulsifier prepared is denoted as emulsifier-5.

[0088] Comparative Example 2

[0089] This comparative example provides a commercially available emulsifier, denoted as Emulsifier-6.

[0090] Performance testing

[0091] Stability test: Emulsions were prepared by adding the emulsifiers from Examples 1-4 and Comparative Examples 1-2 to the formulations shown in Table 1. The preparation steps of the emulsions are as follows:

[0092] 1. Pre-disperse the oil phase and aqueous phase separately;

[0093] 2. Stir and disperse the oil phase with a blunt-tipped impeller at 150-200 rpm, and add the water phase in small batches (multiple times). Each time water is added, it must be emulsified and dispersed evenly.

[0094] 3. After the aqueous phase is completely added, accelerate stirring (1300 rpm) for 10 minutes;

[0095] 4. Add preservatives and flavorings, stir well and it is ready to be discharged.

[0096] The stability of the prepared emulsion was tracked and tested after standing at 60℃ for 24h, 48h, 72h and -15℃ for 24h. The test results are shown in Table 2.

[0097] Table 1 Emulsion Formulation

[0098]

[0099]

[0100] Table 2 Emulsification stability test data

[0101]

[0102] As shown in Table 2, the emulsions prepared by the emulsifiers in Examples 1 to 4 did not exhibit stratification and had good stability.

[0103] Comparative Example 1 is an emulsifier prepared by the polycondensation reaction of glucose with ethylene glycol monoallyl ether and by using an unprotected hydroxyl group on glucose. The emulsion prepared by this emulsion is relatively unstable and will show stratification.

[0104] Compared with the emulsifier prepared by an unknown commercial method in Comparative Example 2, the emulsion prepared by the emulsifier has similar performance at room temperature to that of the emulsifier of this application, but exhibits stratification at low temperature. That is, the emulsifier prepared by the method of this invention not only has similar emulsifying performance at room temperature to that of commercially available emulsifiers, but also has better low-temperature stability and a wider temperature range.

[0105] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a silicone-modified glycoside, characterized by, Includes the following steps: S1 ketones react with hydroxyl groups on carbohydrates in the presence of an acid catalyst to produce an acetal reaction, yielding a reaction system containing carbohydrate intermediates; the carbohydrates are monosaccharides and / or disaccharides. S2. Add a glycidyl ether compound containing a carbon-carbon double bond to the reaction system containing the carbohydrate intermediate obtained in step S1 and heat it to obtain an alkyl glycoside. S3 involves an addition reaction between a hydrosiloxane and the alkyl glycoside obtained in step S2 to obtain an organosilicon-modified glycoside.

2. The preparation method according to claim 1, characterized in that, The glycidyl ether compound containing a carbon-carbon double bond mentioned in step S2 is at least one of allyl glycidyl ether, vinylphenyl glycidyl ether, and o-diallyl bisphenol A diglycidyl ether.

3. The preparation method according to claim 1, characterized in that, In step S2, the amount of glycidyl ether compound containing carbon-carbon double bonds added is based on the molar amount of water produced by the theoretical acetal reaction in S1. The ratio of the number of moles of water produced by the theoretical acetal reaction in S1 to the number of moles of epoxy groups in the glycidyl ether compound containing carbon-carbon double bonds is 1 to 1.3:

1.

4. The preparation method according to claim 1, characterized in that, In step S1, the amount of acidic catalyst added is 0.5 to 1.5 wt% of the reaction system.

5. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. The heating reaction in step S2 is carried out at a temperature of 100–120°C.

6. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. The hydrogen-containing siloxane mentioned in step S3 is at least one of double-ended hydrogen-containing silicone oil, side-chain hydrogen-containing silicone oil, or single-ended hydrogen-containing silicone oil.

7. The method of claim 1, wherein the step of forming the first and second layers is performed by a process selected from the group consisting of: sputtering, evaporation, and chemical vapor deposition. In step S3, the molar ratio of the carbon-carbon double bond group of the alkyl glycoside to the hydrogen-containing group of the hydrogen-containing siloxane is 1:

1.

8. A sugar-modified polyorganosiloxane emulsifier characterized in that, The organosilicon-modified glycoside prepared by the method according to any one of claims 1 to 7 is dispersed in cyclopolydimethylsiloxane, polydimethylsiloxane or isododecane.

9. The sugar-modified polyorganosiloxane emulsifier according to claim 8, characterized in that, The organosilicon-modified glycosides constitute 17–22% by mass in the emulsifier.

10. The use of the emulsifier of claim 9 in daily chemical products.

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