Transparent cationic cellulose and its preparation method and application
A transparent cationic cellulose with both quaternary ammonium salt etherification groups and monoquaternary ammonium salt etherification groups was prepared by subjecting hydroxyethyl cellulose to a dual substitution reaction with quaternary ammonium salt cationic etherification agents. This solved the problems of insufficient transparency and conditioning properties in the prior art and improved the transparency and deposition-promoting ability of shampoo.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROCHEMICAL KUNSHAN CO LTD
- Filing Date
- 2024-12-23
- Publication Date
- 2026-06-23
AI Technical Summary
Existing transparent cationic cellulose is difficult to achieve high transparency and high conditioning performance, and its deposition-promoting ability is insufficient, which cannot meet the demand for highly transparent shampoos.
Hydroxyethyl cellulose was subjected to a di-substitution reaction using bis-quaternary ammonium salt cationic etherifying agents and mono-quaternary ammonium salt cationic etherifying agents to form transparent cationic cellulose with bis-quaternary ammonium salt etherifying groups and mono-quaternary ammonium salt etherifying groups, thereby improving its transparency and conditioning properties.
It achieves high transparency and good conditioning properties, enhances the deposition effect of active factors in shampoo, and improves the overall conditioning performance of shampoo.
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Figure SMS_16 
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Abstract
Description
Technical Field
[0001] This invention relates to the field of shampoo, and more particularly to a transparent cationic cellulose, its preparation method, and its application. Background Technology
[0002] Hair conditioning agents are components used in the formulation of shampoos or conditioners to impart special effects to hair. Along with surfactants, fragrances, and active ingredients, they are an indispensable part of shampoos. They can improve the appearance and feel of hair, making it thicker or softer, and improving the texture of hair damaged by chemical or physical processes.
[0003] The rise of transparent, pure shampoos means that some opaque conditioning ingredients are difficult to add to shampoos, making it harder for them to meet consumer needs in terms of conditioning performance. If active ingredients in shampoos, such as hyaluronic acid and histidine, do not deposit on the hair surface, their effectiveness in revitalizing the hair will be reduced, failing to achieve the desired results.
[0004] Quaternary ammonium cationic cellulose is currently the most widely used hair conditioning agent. However, ordinary cationic cellulose conditioning agents on the market are difficult to achieve the transparency of pure water, their conditioning performance is insufficient, and their deposition-promoting ability needs further improvement. Therefore, it is necessary to develop new hair conditioning agents with high transparency, high conditioning properties, and strong deposition-promoting functions. When applied to shampoos, these agents can be formulated to create highly transparent shampoos with excellent conditioning properties, effectively assisting the deposition of active ingredients in the shampoo onto the hair surface. Summary of the Invention
[0005] This invention provides a transparent cationic cellulose, its preparation method, and its application. While improving the transparency of the transparent cationic cellulose, it also enhances its conditioning and deposition-aiding properties, effectively overcoming the shortcomings of existing technologies.
[0006] One aspect of the present invention provides a transparent cationic cellulose comprising hydroxyethyl cellulose, a bisquaternary ammonium salt etherification group substituted in the hydroxyethyl cellulose, and a monoquaternary ammonium salt etherification group substituted in the hydroxyethyl cellulose, wherein the number of carbon atoms in the bisquaternary ammonium salt etherification group is greater than the number of carbon atoms in the monoquaternary ammonium salt etherification group.
[0007] According to one embodiment of the present invention, the structure of the bisquaternary ammonium salt etherification group is shown in Formula 1:
[0008] Formula 1,
[0009] Wherein, X1 and X2 are each independently selected from Cl and Br, R1 and R2 are each independently selected from alkyl groups having 12 to 16 carbon atoms, n is any integer from 1 to 4, m is any integer from 1 to 4, and t is any integer from 1 to 4; and / or, the structure of the monoquaternary ammonium salt etherification group is as shown in Formula 2:
[0010] Formula 2.
[0011] According to one embodiment of the present invention, the structure of the transparent cationic cellulose is shown in Formula 3:
[0012] Formula 3,
[0013] Wherein, X1 and X2 are each independently selected from Cl and Br, R1 and R2 are each independently selected from alkyl groups having 12 to 16 carbon atoms, n is any integer from 1 to 4, m is any integer from 1 to 4, and t is any integer from 1 to 4.
[0014] Another aspect of the present invention provides a method for preparing transparent cationic cellulose, comprising the following steps: performing a di-substitution reaction on the hydroxyethyl cellulose using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent to obtain the transparent cationic cellulose, wherein the number of carbon atoms of the bis-quaternary ammonium salt cationic etherifying agent is greater than the number of carbon atoms of the mono-quaternary ammonium salt cationic etherifying agent.
[0015] According to one embodiment of the present invention, the preparation method of the bisquaternary ammonium salt cationic etherifying agent includes: reacting a dihaloalkyl alcohol with an alkyl tertiary amine under the action of a first catalyst to obtain an intermediate product, and then reacting the intermediate product with a haloacyl halide under the action of a second catalyst to obtain the bisquaternary ammonium salt cationic etherifying agent, wherein the temperature of the first reaction is higher than the temperature of the second reaction.
[0016] According to one embodiment of the present invention, the structure of the bisquaternary ammonium salt cationic etherifying agent is shown in Formula 4:
[0017] Equation 4,
[0018] Wherein, X1, X2, and X4 are each independently selected from Cl and Br, R1 and R2 are each independently selected from alkyl groups having 12 to 16 carbon atoms, n is any integer from 1 to 4, m is any integer from 1 to 4, and t is any integer from 1 to 4; and / or, the monoquaternary ammonium salt cationic etherifying agent includes 2,3-epoxypropyltrimethylammonium chloride; and / or, the mass ratio of the hydroxyethyl cellulose to the bisquaternary ammonium salt cationic etherifying agent is 1:0.1 to 0.2; and / or, the mass ratio of the hydroxyethyl cellulose to the monoquaternary ammonium salt cationic etherifying agent is 1:0.1 to 0.6.
[0019] According to one embodiment of the present invention, the structure of the dihaloalkyl alcohol is shown in Formula 5:
[0020] Equation 5,
[0021] Wherein, X1 and X2 are each independently selected from Cl and Br, n is any integer from 1 to 4, and m is any integer from 1 to 4; and / or, the structure of the alkyl tertiary amine is as shown in Formula 6:
[0022] Formula 6,
[0023] Wherein, R is selected from any alkyl group having 12 to 16 carbon atoms; and / or, the structure of the haloacyl halide is as shown in Formula 7:
[0024] Equation 7,
[0025] Wherein, X1 and X2 are each independently selected from Cl and Br, and t is any integer from 1 to 4; and / or, the first catalyst includes one or more of potassium iodide and sodium iodide; and / or, the second catalyst includes one or more of triethylamine, sodium carbonate, sodium hydroxide, and potassium carbonate; and / or, the molar ratio of the dihaloalkyl alcohol to the alkyl tertiary amine is 1:1.8-3.0; and / or, the mass ratio of the intermediate product to the haloacyl halide is 1:0.3-1.0.
[0026] According to one embodiment of the present invention, the conditions for the first reaction are: a reaction temperature of 50 ℃ to 70 ℃ and a reaction time of 16 h to 32 h; and / or, the conditions for the second reaction are: a reaction temperature of 0 ℃ to 40 ℃ and a reaction time of 4 h to 12 h.
[0027] According to one embodiment of the present invention, the process of using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent to perform a di-substitution reaction on hydroxyethyl cellulose includes: mixing the bis-quaternary ammonium salt cationic etherifying agent, an inorganic base, a first solvent, and the hydroxyethyl cellulose to perform a first substitution reaction, then adding the mono-quaternary ammonium salt cationic etherifying agent to perform a second substitution reaction to obtain the transparent cationic cellulose.
[0028] According to one embodiment of the present invention, the mass ratio of the hydroxyethyl cellulose to the inorganic base is 1:0.05~0.12; and / or, the conditions for the first substitution reaction are: a reaction temperature of 50 ℃~70 ℃ and a reaction time of 2 h-4 h; and / or, the conditions for the second substitution reaction are: a reaction temperature of 50 ℃~70 ℃ and a reaction time of 3 h-4 h.
[0029] Another aspect of the present invention provides a shampoo comprising the above-described transparent cationic cellulose or transparent cationic cellulose prepared according to the above-described method for preparing transparent cationic cellulose.
[0030] The implementation of this invention has at least the following beneficial effects: By using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent to perform bi-substitution modification on hydroxyethyl cellulose, a transparent cationic cellulose with bis-quaternary ammonium salt etherifying groups and mono-quaternary ammonium salt etherifying groups is obtained, which improves its transparency, conditioning properties and deposition aid properties. Shampoos formulated with transparent cationic cellulose also have high transparency and good conditioning and deposition aid effects. Attached Figure Description
[0031] Figure 1 This is an example of the nuclear magnetic resonance spectrum of hydroxyethyl cellulose and transparent cationic cellulose in one embodiment of the present invention. Detailed Implementation
[0032] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.
[0033] This invention provides a transparent cationic cellulose, comprising hydroxyethyl cellulose, a bisquaternary ammonium salt etherification group substituted with hydroxyethyl cellulose, and a monoquaternary ammonium salt etherification group substituted with hydroxyethyl cellulose, wherein the number of carbon atoms in the bisquaternary ammonium salt etherification group is greater than the number of carbon atoms in the monoquaternary ammonium salt etherification group.
[0034] According to the inventors' research, the bis-quaternary ammonium salt etherification group and the mono-quaternary ammonium salt etherification group improve the transparency, conditioning properties and deposition aid properties of transparent cationic cellulose.
[0035] Specifically, the number of carbon atoms in the bisquaternary ammonium salt etherification group is greater than or equal to 34, and can be any integer from 34 to 60, such as any integer in the range of 34, 35, 38, 40, 42, 45, 50, 55, 60 or any combination thereof.
[0036] Specifically, the number of carbon atoms in the monoquaternary ammonium salt etherification group is less than or equal to 10, specifically 5 to 10, for example 5, 6, 7, 8, 9, or 10. The difference between the number of carbon atoms in the bisquaternary ammonium salt etherification group and the number of carbon atoms in the monoquaternary ammonium salt etherification group is any integer from 18 to 54, for example, any integer within the range of 18, 20, 25, 30, 35, 40, 45, 50, 54, or any combination thereof.
[0037] In some embodiments, the structure of the bisquaternary ammonium salt etherification group is shown in Formula 1:
[0038] Formula 1,
[0039] Wherein, X1 and X2 are each independently selected from Cl and Br, and R1 and R2 are each independently selected from any alkyl group having 12 to 16 carbon atoms, specifically any alkyl group having an even number of carbon atoms from 12 to 16, such as dodecyl, tetradecyl, and hexadecyl. n is any integer from 1 to 4, such as 1, 2, 3, and 4. m is any integer from 1 to 4, such as 1, 2, 3, and 4. t is any integer from 1 to 4, such as 1, 2, 3, and 4.
[0040] In some embodiments, the structure of the monoquaternary ammonium salt etherification group is shown in Formula 2:
[0041] Formula 2.
[0042] In some embodiments, the structure of transparent cationic cellulose is shown in Formula 3:
[0043] Formula 3,
[0044] Wherein, X1 and X2 are each independently selected from Cl and Br, and R1 and R2 are each independently selected from alkyl groups with 12 to 16 carbon atoms, specifically from alkyl groups with an even number of carbon atoms from 12 to 16, such as dodecyl, tetradecyl, and hexadecyl. n is any integer from 1 to 4, such as 1, 2, 3, and 4. m is any integer from 1 to 4, such as 1, 2, 3, and 4. t is any integer from 1 to 4, such as 1, 2, 3, and 4.
[0045] This invention also provides a method for preparing transparent cationic cellulose, comprising the following steps: using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent to perform a di-substitution reaction on hydroxyethyl cellulose to obtain transparent cationic cellulose; the number of carbon atoms in the bis-quaternary ammonium salt etherifying agent is greater than the number of carbon atoms in the mono-quaternary ammonium salt etherifying agent, which is beneficial for the formation of bis-quaternary ammonium salt etherifying groups and mono-quaternary ammonium salt etherifying groups in transparent cationic cellulose.
[0046] Specifically, the bisquaternary ammonium salt cationic etherifying agent is a gemini-type bisquaternary ammonium salt long-chain cationic etherifying agent (or gemini-type bisquaternary ammonium salt long-chain hydrophobic cationic etherifying agent), used to form bisquaternary ammonium salt etherification groups in transparent cationic cellulose. The number of carbon atoms in the bisquaternary ammonium salt cationic etherifying agent is greater than or equal to 34, and can be any integer from 34 to 60, such as any integer in the range of 34, 35, 38, 40, 42, 45, 50, 55, 60 or any combination thereof.
[0047] Specifically, the monoquaternary ammonium salt cationic etherifying agent is a monoquaternary ammonium salt non-long-chain cationic etherifying agent (or monoquaternary ammonium salt non-long-chain non-hydrophobic cationic catalyst) used to form monoquaternary ammonium salt etherification groups in transparent cationic cellulose. The number of carbon atoms in the monoquaternary ammonium salt cationic etherifying agent is less than or equal to 10, specifically 5 to 10, such as 5, 6, 7, 8, 9, and 10.
[0048] In practice, the difference between the number of carbon atoms in the bis-quaternary ammonium salt cationic etherifying agent and the number of carbon atoms in the mono-quaternary ammonium salt cationic etherifying agent is any integer from 18 to 54, such as any integer in the range of 18, 20, 25, 30, 35, 40, 45, 50, 54 or any two of them.
[0049] In some embodiments, the preparation method of the bisquaternary ammonium salt cationic etherifying agent includes: reacting a dihaloalkyl alcohol with an alkyl tertiary amine under the action of a first catalyst to obtain an intermediate product; and then reacting the intermediate product with a haloacyl halide under the action of a second catalyst to obtain the bisquaternary ammonium salt cationic etherifying agent, wherein the temperature of the first reaction is higher than the temperature of the second reaction.
[0050] In practice, a dihaloalkyl alcohol, an alkyl tertiary amine, and a second solvent are added sequentially to a three-necked flask and stirred until completely dissolved. Then, a first catalyst is added to carry out the first reaction. After the reaction is completed, the second solvent is removed by vacuum distillation, petroleum ether is added and filtered, and the product is dried under vacuum to obtain an intermediate product. Then, the intermediate product, the second catalyst, and the third solvent are added sequentially to a three-necked flask, and a haloacyl halide is added to carry out the second reaction. The product is washed with dilute hydrochloric acid and pure water, dried with anhydrous sodium sulfate, filtered, and distilled under vacuum to obtain a bisquaternary ammonium salt cationic etherifying agent.
[0051] Specifically, the second solvent includes organic solvents, specifically alcohol solvents, which may include ethanol; the third solvent includes organic solvents, specifically haloalkane solvents, which may include chloroform.
[0052] In some embodiments, the structure of the bisquaternary ammonium salt cationic etherifying agent is shown in Formula 4:
[0053] Equation 4,
[0054] X1, X2, and X4 are each independently selected from Cl and Br, and R1 and R2 are each independently selected from alkyl groups with 12 to 16 carbon atoms, specifically from alkyl groups with an even number of carbon atoms from 12 to 16, such as dodecyl, tetradecyl, and hexadecyl. n is any integer from 1 to 4, such as 1, 2, 3, and 4. m is any integer from 1 to 4, such as 1, 2, 3, and 4. t is any integer from 1 to 4, such as 1, 2, 3, and 4. These are used to form a bisquaternary ammonium salt etherification group substituted for hydroxyethyl cellulose.
[0055] In some embodiments, the monoquaternary ammonium salt cationic etherifying agent includes 2,3-epoxypropyltrimethylammonium chloride, which is used to form a monoquaternary ammonium salt etherifying group substituted with hydroxyethyl cellulose, and to perform a double substitution reaction in combination with a bisquaternary ammonium salt cationic etherifying agent, thereby increasing the degree of substitution of transparent cationic cellulose and further improving its conditioning and deposition aid functions.
[0056] In some embodiments, the mass ratio of hydroxyethyl cellulose to the bisquaternary ammonium cationic etherifying agent is 1:0.1 to 0.2, for example, 1:0.11, 1:0.12, 1:0.13, 1:0.14, 1:0.15, 1:0.6, 1:0.17, 1:0.18, 1:0.19, 1:0.2, or any combination thereof.
[0057] In some embodiments, the mass ratio of hydroxyethyl cellulose to monoquaternary ammonium salt cationic etherifying agent is 1:0.1 to 0.6, for example, a range consisting of 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6 or any two of these.
[0058] In some embodiments, the structure of the dihaloalkyl alcohol is shown in Formula 5:
[0059] Equation 5,
[0060] Where X1 and X2 are each independently selected from either Cl or Br, n is any integer from 1 to 4, for example 1, 2, 3, 4, m is any integer from 1 to 4, for example 1, 2, 3, 4, and t is any integer from 1 to 4, for example 1, 2, 3, 4.
[0061] In some embodiments, the structure of the alkyl tertiary amine is shown in Formula 6:
[0062] Formula 6,
[0063] Wherein, R is any one of the alkyl groups having 12 to 16 carbon atoms, specifically selected from any one of the even-numbered alkyl groups having 12 to 16 carbon atoms, such as dodecyl, tetradecyl, and hexadecyl.
[0064] In some embodiments, the structure of the haloacyl halide is shown in Formula 7:
[0065] Equation 7,
[0066] X1 and X2 are each independently selected from either Cl or Br, and t is any integer from 1 to 4, such as 1, 2, 3, or 4.
[0067] In practice, halogenated acyl halides include halogenated acyl chlorides.
[0068] In some embodiments, the first catalyst includes one or more of potassium iodide and sodium iodide; the second catalyst includes one or more of triethylamine, sodium carbonate, sodium hydroxide, and potassium carbonate, which is beneficial to improving the synthesis efficiency of the bisquaternary ammonium salt cationic etherifying agent.
[0069] In some embodiments, the molar ratio of the dihaloalkyl alcohol to the alkyl tertiary amine is 1:1.8-3.0, for example, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8, 1:2.9, 1:3.0 or any combination thereof.
[0070] Furthermore, a mass ratio of intermediate product to haloacyl chloride halogen of 1:0.3 to 1.0, such as 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0 or any combination thereof, is favorable for the synthesis of bisquaternary ammonium salt cationic etherifying agents.
[0071] In some embodiments, the reaction temperature of the first reaction is 50 ℃ to 70 ℃, for example, a range of 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or any two of these.
[0072] Furthermore, the reaction time of the first reaction is 16 h to 32 h, such as 16 h, 18 h, 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, 32 h or any combination thereof, which is conducive to the full reaction of dihaloalkyl alcohols with alkyl tertiary amines and the formation of intermediate products.
[0073] In some embodiments, the reaction temperature of the second reaction is 0 ℃ to 40 ℃, for example, a range of 0 ℃, 5 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃ or any combination thereof.
[0074] Furthermore, the reaction time of the second reaction is 4 h to 12 h, for example, a range of 4 h, 6 h, 8 h, 10 h, 12 h or any combination thereof, which is conducive to the reaction of the intermediate product with the haloacyl halide and the generation of the bisquaternary ammonium salt cationic etherifying agent.
[0075] In some embodiments, the process of performing a di-substitution reaction of hydroxyethyl cellulose using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent includes: mixing the bis-quaternary ammonium salt cationic etherifying agent, an inorganic base, a first solvent, and hydroxyethyl cellulose to perform a first substitution reaction, then adding the mono-quaternary ammonium salt cationic etherifying agent to perform a second substitution reaction to obtain transparent cationic cellulose.
[0076] In practice, the bisquaternary ammonium salt cationic etherifying agent is prepared into an aqueous solution. Under the condition of maintaining a water bath at 20 ℃, the first solvent, the inorganic base aqueous solution, and the bisquaternary ammonium salt cationic etherifying agent aqueous solution are added sequentially to a three-necked flask. After stirring for 5 min, hydroxyethyl cellulose is added, and the mixture is stirred at 20 ℃ for 30 min to carry out the first substitution reaction. After the reaction is completed, the mixture is cooled to 20 ℃, and the monoquaternary ammonium salt cationic etherifying agent aqueous solution is added. The mixture is stirred at 20 ℃ for 30 min to carry out the second substitution reaction. After the reaction is completed, the mixture is filtered, washed with isopropanol, vacuum dried, and pulverized to obtain transparent cationic cellulose.
[0077] Specifically, the mass percentage of the monoquaternary ammonium salt cationic etherifying agent in the aqueous solution of the monoquaternary ammonium salt cationic etherifying agent is 40% to 70%, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70% or any combination thereof. The monoquaternary ammonium salt cationic etherifying agent is uniformly dispersed in the aqueous solution, which is beneficial to improving the efficiency of the second substitution reaction.
[0078] In practice, the inorganic base includes hydroxides, which may include sodium hydroxide; the first solvent includes organic solvents, specifically alcohol solvents, which may include isopropanol.
[0079] In some embodiments, the mass ratio of hydroxyethyl cellulose to inorganic alkali is 1:0.05 to 0.12, for example, a range consisting of 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.10, 1:0.11, 1:0.12, or any two of these.
[0080] In some embodiments, the reaction temperature of the first substitution reaction is 50 °C to 70 °C, for example, a range consisting of 50 °C, 55 °C, 60 °C, 65 °C, 70 °C or any two thereof; and the reaction time is 3 h to 4 h, for example, a range consisting of 3 h, 3.2 h, 3.4 h, 3.5 h, 3.6 h, 3.8 h, 4 h or any two thereof.
[0081] Furthermore, the reaction temperature of the second substitution reaction is 50 ℃ to 70 ℃, for example, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ or any combination thereof; the reaction time is 3 h to 4 h, for example, 3 h, 3.2 h, 3.4 h, 3.5 h, 3.6 h, 3.8 h, 4 h or any combination thereof.
[0082] This invention also provides a shampoo comprising the above-mentioned transparent cationic cellulose or transparent cationic cellulose prepared by the above-mentioned method for preparing transparent cationic cellulose, which has the same advantages as transparent cationic cellulose, and will not be described in detail here.
[0083] In some embodiments, the shampoo also includes active ingredients, including hyaluronic acid and histidine.
[0084] The present invention will be further described below through specific embodiments.
[0085] The raw materials used in the examples and comparative examples are as follows: hydroxyethyl cellulose (HEC) was purchased from North Tianpu; all other reagents were purchased from Aladdin Company.
[0086] Example 1
[0087] The transparent cationic cellulose of this embodiment 1 includes a hydroxyethyl cellulose substrate, a bisquaternary ammonium salt etherification group substituted for hydroxyethyl cellulose, and a monoquaternary ammonium salt etherification group substituted for hydroxyethyl cellulose, the structure of which is shown in Formula 1 below.
[0088] Formula 1,
[0089] In this system, X1 and X2 are both Cl, R1 and R2 are both dodecyl groups with 12 carbon atoms, n is 1, m is 1, and t is 2.
[0090] The preparation process of the transparent cationic cellulose in Example 1 is as follows:
[0091] (1) Preparation of bisquaternary ammonium salt cationic etherifying agent
[0092] In a three-necked flask, 3.87 g (30 mmol) of 1,3-dichloro-2-propanol, 12.78 g (60 mmol) of N,N-dimethyldodecylamine, and 30 g of anhydrous ethanol were added sequentially. The mixture was stirred until completely dissolved, potassium iodide was added, and the temperature was raised to 65 °C. The reaction was carried out for 16 h. The ethanol was removed by vacuum distillation, and the product was filtered after adding petroleum ether and dried under vacuum to obtain the intermediate product. Then, 14 g of the intermediate product, 5 g (50 mmol) of triethylamine, and 30 g of chloroform were added sequentially to the three-necked flask. 6.4 g (50 mmol) of 3-chloropropionyl chloride was added dropwise at 5 °C. After the addition was complete, the product was reacted for 6 h. The product was washed with dilute hydrochloric acid and pure water, dried over anhydrous sodium sulfate, filtered, and then distilled under vacuum to obtain the bisquaternary ammonium salt cationic etherifying agent.
[0093] (2) Preparation of transparent cationic cellulose
[0094] A 50% aqueous solution of the bisquaternary ammonium salt cationic etherifying agent was prepared. The solution was kept at 20 °C in a water bath. 150 g of isopropanol, 12 g of sodium hydroxide aqueous solution (30% mass concentration), and 10 g of the bisquaternary ammonium salt cationic etherifying agent aqueous solution (50% mass concentration) were added sequentially to a three-necked flask and stirred for 5 min. Then, 50 g of hydroxyethyl cellulose was added, and the mixture was stirred at 20 °C for 30 min. The temperature was then increased to 65 °C, and the reaction was allowed to proceed for 3 h. The mixture was then cooled to 20 °C. Next, 17.5 g of 2,3-epoxypropyltrimethylammonium chloride aqueous solution (50% mass concentration) was added dropwise. After the addition was complete, the mixture was stirred at 20 °C for 30 min, and the temperature was increased to 65 °C. The reaction was allowed to proceed for 3 h. The mixture was then filtered, washed with an 80% isopropanol aqueous solution, vacuum dried, and pulverized to obtain transparent cationic cellulose. Nuclear magnetic resonance (NMR) spectroscopy confirmed that the bisquaternary ammonium salt etherifying groups and monoquaternary ammonium salt etherifying groups substituted for the hydroxyethyl cellulose. The results are shown in [Figure number missing]. Figure 1 Compared with unsubstituted hydroxyethyl cellulose, transparent cationic cellulose has additional group peaks at chemical shifts of 0–2 ppm and 4.4–4.6 ppm. The peaks at chemical shifts of 0–2 ppm are the methyl and methylene peaks of the substituted bisquaternary ammonium salt etherification groups, and the peaks at chemical shifts of 4.4–4.6 ppm are the hydrogen atom peaks on the carbon atoms attached to the hydroxyl groups of the substituted monoquaternary ammonium salt etherification groups.
[0095] Comparative Example 1
[0096] Maintaining a water bath temperature of 20 °C, 150 g of isopropanol, 12 g of sodium hydroxide aqueous solution (30% mass concentration), and 17.5 g of 2,3-epoxypropyltrimethylammonium chloride aqueous solution (50% mass concentration) were added sequentially to a three-necked flask and stirred for 5 min. Then, 50 g of hydroxyethyl cellulose was added, and the mixture was stirred at 20 °C for 30 min. The temperature was then increased to 65 °C, and the reaction was carried out for 3 h. The mixture was then filtered, washed with isopropanol aqueous solution (80% mass concentration), vacuum dried, and pulverized to obtain cationic cellulose substituted with a monoquaternary ammonium salt cationic etherifying agent.
[0097] Comparative Example 2
[0098] (1) Preparation of bisquaternary ammonium salt cationic etherifying agent
[0099] Same as Example 1
[0100] (2) Preparation of cationic cellulose
[0101] A 50% aqueous solution of the bisquaternary ammonium salt cationic etherifying agent was prepared. The solution was kept at 20 °C in a water bath. 150 g of isopropanol, 12 g of sodium hydroxide aqueous solution (30% mass concentration), and 10 g of the bisquaternary ammonium salt cationic etherifying agent (50% mass concentration) were added sequentially to a three-necked flask and stirred for 5 min. Then, 50 g of hydroxyethyl cellulose was added, and the mixture was stirred at 20 °C for 30 min. The temperature was then increased to 65 °C, and the reaction was allowed to proceed for 3 hours. The mixture was then filtered, washed with an isopropanol aqueous solution (80% mass concentration), vacuum dried, and pulverized to obtain cationic cellulose substituted with the bisquaternary ammonium salt cationic etherifying agent.
[0102] The transparent cationic cellulose of Examples 1-7 and the cationic cellulose of Comparative Examples 1-2 were tested for performance using the following procedures. The results are shown in Table 1:
[0103] (1) Test of cationic cellulose transmittance: The cationic cellulose obtained in the examples and comparative examples was prepared into a solution with a mass concentration of 0.5% by pure water. The solution was placed in the sample cell of the visible-ultraviolet spectrophotometer and the wavelength of 550 nm was selected for measurement.
[0104] (2) Shampoo preparation
[0105] Silicone-free, easy-to-formulate shampoo: Dissolve 0.5 g of cationic cellulose in 30 g of water to form phase A; stir 15 g of sodium lauryl ether sulfate (AES), 3 g of cocamidopropyl betaine (CAPB), and 50 g of water at 80°C until dissolved to form phase B; cool phase B to 50°C, add phase A, and continue stirring until completely dissolved.
[0106] Simple preparation process for silicone-containing shampoo: Dissolve 0.5 g cationic cellulose in 30 g water to form phase A; stir 15 g AES, 3 g CAPB, and 50 g water at 80 ℃ until dissolved to form phase B; cool phase B to 50 ℃, add phase A and 1 g silicone oil, and continue stirring until completely dissolved.
[0107] (3) Shampoo transmittance test: The prepared silicone-free simple shampoo was placed in the sample cell of the visible-ultraviolet spectrophotometer and the wavelength of 550 nm was selected for measurement.
[0108] (4) Wet combing performance test method for shampoo: First, wet real human hair that has not been chemically treated such as perming, dyeing or bleaching with warm water at about 40 ℃. Then, wash it with a 10 wt% sodium lauryl sulfate (K12) aqueous solution, rubbing it on both sides for half a minute. Then rinse with warm water to remove the foam. Use a syringe to draw 2 mL of the prepared silicone-free simple shampoo to wash the hair. After washing, use two fingers to remove the water along the hair strands. Use a hair combing instrument to test the wet combing performance.
[0109] (5) Test method for silicone oil deposition in shampoo: First, wet real human hair that has not been chemically treated such as perming, dyeing, or bleaching with warm water at about 40 ℃. Then, wash it with 10 wt% K12 solution, rubbing both sides for half a minute. Rinse with warm water to remove foam. Use a syringe to draw 2 mL of the prepared silicone oil-containing simple shampoo to wash the hair. After washing, use two fingers to remove water along the hair strand and place it in an artificial climate chamber to dry. After the hair strand is dry, take 0.100-0.120 g of hair sample, digest it using a fully automated digester, and then load the sample onto inductively coupled plasma (ICP) to analyze the silicon element.
[0110] Table 1
[0111]
[0112] As can be seen from Table 1, compared with Comparative Examples 1 and 2, the difference in Example 1 is that hydroxyethyl cellulose is disubstituted with bis-quaternary ammonium salt cationic etherifying agents and mono-quaternary ammonium salt cationic etherifying agents to prepare transparent cationic cellulose containing bis-quaternary ammonium salt etherifying groups and mono-quaternary ammonium salt etherifying groups. This improves the light transmittance to 99.5%, which is close to pure water. It also improves the light transmittance of shampoos formulated with transparent cationic cellulose, which is beneficial for reducing wet combing work and improving the ability to assist silicone oil deposition, thereby improving conditioning and deposition performance.
[0113] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.
Claims
1. A transparent cationic cellulose, characterized in that, It includes hydroxyethyl cellulose, and a bisquaternary ammonium salt etherification group substituted in the hydroxyethyl cellulose and a monoquaternary ammonium salt etherification group substituted in the hydroxyethyl cellulose, wherein the number of carbon atoms in the bisquaternary ammonium salt etherification group is greater than the number of carbon atoms in the monoquaternary ammonium salt etherification group.
2. The transparent cationic cellulose according to claim 1, characterized in that, The structure of the bisquaternary ammonium salt etherification group is shown in Formula 1: Formula 1, Wherein, X1 and X2 are each independently selected from Cl and Br, R1 and R2 are each independently selected from alkyl groups having 12 to 16 carbon atoms, n is any integer from 1 to 4, m is any integer from 1 to 4, and t is any integer from 1 to 4. And / or, the structure of the monoquaternary ammonium salt etherification group is shown in Formula 2: Formula 2.
3. The transparent cationic cellulose according to claim 1, characterized in that, The structural formula of the transparent cationic cellulose is shown in Figure 3: Formula 3, Wherein, X1 and X2 are each independently selected from Cl and Br, R1 and R2 are each independently selected from alkyl groups having 12 to 16 carbon atoms, n is any integer from 1 to 4, m is any integer from 1 to 4, and t is any integer from 1 to 4.
4. A method for preparing transparent cationic cellulose according to any one of claims 1-3, characterized in that, Includes the following steps: The hydroxyethyl cellulose was subjected to a di-substitution reaction using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent to obtain the transparent cationic cellulose. The number of carbon atoms in the bis-quaternary ammonium salt cationic etherifying agent was greater than the number of carbon atoms in the mono-quaternary ammonium salt cationic etherifying agent.
5. The method for preparing transparent cationic cellulose according to claim 4, characterized in that, The preparation method of the bisquaternary ammonium salt cationic etherifying agent includes: reacting a dihaloalkyl alcohol with an alkyl tertiary amine under the action of a first catalyst to obtain an intermediate product, and then reacting the intermediate product with a haloacyl halide under the action of a second catalyst to obtain the bisquaternary ammonium salt cationic etherifying agent, wherein the temperature of the first reaction is higher than the temperature of the second reaction.
6. The method for preparing transparent cationic cellulose according to claim 4, characterized in that, The structure of the bisquaternary ammonium salt cationic etherifying agent is shown in Formula 4: Equation 4, Wherein, X1, X2, and X4 are each independently selected from Cl and Br, R1 and R2 are each independently selected from alkyl groups having 12 to 16 carbon atoms, n is any integer from 1 to 4, m is any integer from 1 to 4, and t is any integer from 1 to 4. And / or, the monoquaternary ammonium salt cationic etherifying agent comprises 2,3-epoxypropyltrimethylammonium chloride; And / or, the mass ratio of the hydroxyethyl cellulose to the bisquaternary ammonium salt cationic etherifying agent is 1:0.1~0.2; And / or, the mass ratio of the hydroxyethyl cellulose to the monoquaternary ammonium salt cationic etherifying agent is 1:0.1~0.
6.
7. The method for preparing transparent cationic cellulose according to claim 5, characterized in that, The structure of the dihaloalkyl alcohol is shown in Formula 5: Equation 5, Where X1 and X2 are each independently selected from either Cl or Br, n is any integer from 1 to 4, and m is any integer from 1 to 4; And / or, the structure of the alkyl tertiary amine is shown in Formula 6: Formula 6, Wherein, R is selected from any one of alkyl groups having 12 to 16 carbon atoms; And / or, the structure of the haloacyl halogen is as shown in Formula 7: Equation 7, Where X1 and X2 are each independently selected from either Cl or Br, and t is any integer from 1 to 4; And / or, the first catalyst includes one or more of potassium iodide and sodium iodide; And / or, the second catalyst comprises one or more of triethylamine, sodium carbonate, sodium hydroxide, and potassium carbonate; And / or, the molar ratio of the dihaloalkyl alcohol to the alkyl tertiary amine is 1:1.8-3.0; And / or, the mass ratio of the intermediate product to the haloacyl halide is 1:0.3~1.
0.
8. The method for preparing transparent cationic cellulose according to claim 5, characterized in that, The conditions for the first reaction are: reaction temperature of 50 ℃~70 ℃, and reaction time of 16 h~32 h; And / or, the conditions for the second reaction are: a reaction temperature of 0 ℃ to 40 ℃ and a reaction time of 4 h to 12 h.
9. The method for preparing transparent cationic cellulose according to claim 4, characterized in that, The process of using a bis-quaternary ammonium salt cationic etherifying agent and a mono-quaternary ammonium salt cationic etherifying agent to perform a di-substitution reaction on hydroxyethyl cellulose includes: mixing the bis-quaternary ammonium salt cationic etherifying agent, an inorganic base, a first solvent, and the hydroxyethyl cellulose to perform a first substitution reaction; then adding the mono-quaternary ammonium salt cationic etherifying agent to perform a second substitution reaction to obtain the transparent cationic cellulose.
10. The method for preparing transparent cationic cellulose according to claim 9, characterized in that, The mass ratio of the hydroxyethyl cellulose to the inorganic base is 1:0.05~0.12; And / or, the conditions for the first substitution reaction are: a reaction temperature of 50 ℃~70 ℃ and a reaction time of 2 h-4 h; And / or, the conditions for the second substitution reaction are: a reaction temperature of 50 ℃ to 70 ℃ and a reaction time of 3 h to 4 h.
11. A shampoo, characterized in that, This includes the transparent cationic cellulose according to any one of claims 1-3 or the transparent cationic cellulose prepared according to the preparation method of the transparent cationic cellulose according to any one of claims 4-10.