A process for the production of polyquaternium-10

Abstract

The application discloses a kind of polyquaternary ammonium salt-10 and the method for producing polyquaternary ammonium salt-10, comprising the following steps: by salt removal method in isopropanol Etherification agent 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and lye reaction is generated and the sodium chloride solid that separates out is filtered out, and is reacted with hydroxyethyl cellulose, after washing, filtration, accurately determine the end point of washing by conductivity method, then dry, crush, obtain polyquaternary ammonium salt-10 product.The method for producing polyquaternary ammonium salt-10 of the application significantly reduces the impurity salt content in the reaction process, reduces the corrosion risk of equipment, reduces the solvent consumption when washing, determines the end point of washing, improves the post-treatment and production efficiency, and is suitable for industrial production.

Description

Technical Field

[0001] This invention relates to a method for producing polyquaternium-10, belonging to the field of natural cellulose derivatives. Background Technology

[0002] Polyquaternium-10 is a product obtained by quaternization modification of hydroxyethyl cellulose. It possesses both the cationic properties of quaternium salts and the good film-forming and water-soluble properties of cellulose. It is mainly used in various shampoos, conditioners, and other personal care products, providing unique antistatic, combing, and repairing properties. Polyquaternium-10 products are natural polymer derivatives, non-toxic and non-irritating to the human body. A small amount added to shampoo can produce significant effects. Currently, it is widely used in various types of shampoos on the market, including popular transparent shampoos and silicone-free shampoos.

[0003] The production of polyquaternium-10 involves adding hydroxyethyl cellulose, alkaline solution, and cationic etherifying agent to an alcohol-water system and carrying out an etherification reaction at a certain temperature and time. After adding an appropriate amount of acid to adjust the system to a weakly acidic state, the reaction is stopped. The finished product is then obtained after post-processing such as washing, drying, and pulverizing.

[0004] However, current production processes for preparing polyquaternary ammonium salt-10 products introduce additional chloride ions during the reaction, increasing the risk of corrosion. Alternatively, the use of novel etherifying agents such as glycidyltrimethylammonium chloride presents challenges due to its susceptibility to deactivation, difficulty in storage, and significant increases in production costs. Furthermore, the quality of the resulting products is inconsistent. Therefore, a new process is needed to address the issue of chloride ions introduced by the etherifying agent, while simultaneously achieving stable product quality, saving on washing solvents, and reducing production costs. It is hoped that this new process will overcome the various shortcomings of existing technologies. Summary of the Invention

[0005] To overcome the shortcomings of existing processes, this invention provides a new method for producing polyquaternium-10. This process can reduce the content of sodium chloride impurities during the reaction, reduce the amount of detergent used in post-treatment, and quickly determine the washing endpoint, thereby achieving the goal of stabilizing product quality and reducing production costs.

[0006] In another aspect of the present invention, a polyquaternium-10 product produced by the aforementioned method is provided.

[0007] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:

[0008] A method for producing polyquaternium-10 includes the following steps:

[0009] (1) Desalination: In an inert gas environment, a solvent is added to the reactor, and a cationic etherifying agent and a small excess of alkaline solution are added under stirring. The mixture is stirred until white granular sodium chloride solid is gradually produced in the reaction system. The white solid is filtered and the reaction solution is retained.

[0010] (2) Add hydroxyethyl cellulose to the reaction solution of step (1) and react. After the reaction is completed, add a terminator to stop the reaction.

[0011] (3) Filter the reaction product obtained in step (2), wash and filter repeatedly, and use a conductivity meter to monitor the conductivity of the filtrate after washing. When the conductivity reaches 300-350 μS / cm, it is the washing endpoint. Dry and pulverize the filtered substance to obtain polyquaternium-10 product.

[0012] In some specific embodiments, the solvent is a small molecule alcohol, such as ethanol, propanol, butanol, isopropanol, etc., preferably isopropanol; and / or

[0013] The cationic etherifying agent is 3-chloro-2-hydroxypropyltrimethylammonium chloride, glycidyltrimethylammonium chloride, any one of a halogenated quaternary ammonium salt or an epoxy quaternary ammonium salt, preferably 3-chloro-2-hydroxypropyltrimethylammonium chloride; and / or

[0014] The terminating agent is an acid terminating agent, such as hydrochloric acid, formic acid, acetic acid, etc., preferably acetic acid.

[0015] In some specific embodiments, the 3-chloro-2-hydroxypropyltrimethylammonium chloride is an aqueous solution with a mass concentration of 1-69 wt%, preferably 69 wt%; and / or

[0016] The alkaline solution is any one of an aqueous solution of sodium hydroxide, potassium hydroxide, or ammonia, preferably with a mass concentration of 10-30 wt%, and more preferably 13 wt%.

[0017] In some specific implementation schemes, with 1 part of hydroxyethyl cellulose, the amount of solvent in step (1) is 6-8 parts, the amount of cationic etherifying agent is 0.8-1.1 parts, and the amount of alkali solution is 1.3-1.7 parts;

[0018] Preferably, step (1) is performed at room temperature and pressure.

[0019] In some specific implementation schemes, the reaction in step (2) is carried out at a temperature of 40-60°C for 4-6 hours.

[0020] In some specific implementation schemes, the amount of acetic acid used in step (2) is 0.05-0.07 parts, which is based on 1 part of hydroxyethyl cellulose.

[0021] In some specific implementations, the washing in step (3) uses an aqueous solution of isopropanol with a mass concentration of 80 wt%.

[0022] In some specific implementations, the amount of the 80% isopropanol aqueous solution is 8-10 parts, with 1 part of hydroxyethyl cellulose used.

[0023] In another aspect of the present invention, the polyquaternium-10 product is a high-nitrogen polyquaternium-10 with a nitrogen content of 1.5-2.2 wt%.

[0024] In some specific implementations, the polyquaternium-10 product contains <1 wt% sodium ions and <5.5 wt% free chloride ions.

[0025] Compared with the prior art, the present invention has the following outstanding advantages and beneficial effects:

[0026] This invention solves the problem of sodium chloride impurities introduced when using stable and lower-cost etherifying agents such as 3-chloro-2-hydroxypropyltrimethylammonium chloride as etherifying agents by employing a desalination method. This new process removes most of the sodium chloride, reducing the risk of equipment corrosion. Furthermore, the pre-desalination reduces the amount of detergent used in the subsequent washing process, saving production costs. This invention uses the conductivity method to determine the washing endpoint in the subsequent washing process. This method is simple, stable, and reliable, reducing additional detergent consumption and improving production efficiency.

[0027] The polyquaternary ammonium salt-10 product of this invention has a sodium ion content of <1wt% and a free chloride ion content of <5.5wt%. Detailed Implementation

[0028] To better understand the technical solution of the present invention, the following embodiments will further illustrate the method provided by the present invention. However, the present invention is not limited to the listed embodiments, but should also include any other known modifications within the scope of the claims of the present invention.

[0029] The method of this invention cleverly employs a desalination method to pre-remove most of the sodium chloride impurities introduced by using 3-chloro-2-hydroxypropyltrimethylammonium chloride as an etherifying agent. Taking 3-chloro-2-hydroxypropyltrimethylammonium chloride as an etherifying agent as an example, the principle of the desalination method is to react 3-chloro-2-hydroxypropyltrimethylammonium chloride with a slightly excess aqueous solution of sodium hydroxide in a large amount of isopropanol, thereby generating the active component glycidyltrimethylammonium chloride and the impurity sodium chloride. The active component, quaternary ammonium salt, preferentially dissolves in water in the alcohol-water system, causing the system to separate into layers. Some of the quaternary ammonium salt also dissolves in isopropanol, while sodium chloride is insoluble in isopropanol and its solubility in water is much lower than that of the quaternary ammonium salt. Therefore, under a certain alcohol-water ratio, when the quaternary ammonium salt is saturated and dissolved in water, it will force the sodium chloride to precipitate. Most of the sodium chloride in the system can be removed by filtration. At the same time, the slightly excess sodium hydroxide makes the system neutral to weakly alkaline. Under these conditions, the active component glycidyltrimethylammonium chloride is relatively stable and can then be used in the next etherification reaction.

[0030] This invention also innovatively introduces the conductivity method to quickly calibrate the washing endpoint in the post-treatment washing stage. The principle is that the washing mainly targets impurities such as sodium chloride and quaternary ammonium salts in the production process. The amount of impurities will cause changes in the conductivity of the washing filtrate. By monitoring and calibrating the changes in conductivity, the washing endpoint can be determined.

[0031] By way of example, a method for producing polyquaternium-10 according to the present invention includes the following steps:

[0032] (1) Desalination: Isopropanol is added under normal temperature and pressure and in an inert gas environment. Under stirring conditions, etherifying agent 3-chloro-2-hydroxypropyltrimethylammonium chloride and alkaline solution are added simultaneously and evenly. After stirring for 10-15 minutes, white granular sodium chloride solid will gradually be generated in the reaction system. After filtering the white solid, the reaction solution is retained.

[0033] (2) Add hydroxyethyl cellulose to the reaction solution in step (1) and react at 40-60℃ (e.g., 45℃, 50℃, 55℃, etc.) for 4-6 hours, e.g., 4.5 hours, 5 hours, 5.5 hours, etc. After the reaction is completed, add acetic acid to stop the reaction;

[0034] (3) Filter the substance obtained in step (2), wash and filter it 2-3 times with an isopropanol aqueous solution with a mass concentration of 80wt.%. Use a conductivity meter to test the conductivity of the filtrate after washing. When the conductivity reaches 300-350μS / cm (e.g., 300μS / cm, 310μS / cm, 320μS / cm, 330μS / cm, 340μS / cm, 350μS / cm, etc.), it is the washing endpoint. Then dry and pulverize the filtered substance to obtain the polyquaternium-10 product.

[0035] The filtration, drying, and pulverization processes are all conventional techniques in this field, and this invention does not impose any particular limitations; existing technologies can be referenced. Specifically, for example, the drying temperature is 60-100℃, and the drying time is 2-8 hours.

[0036] In this invention, the cationic etherifying agent is preferably a 69 wt% aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride, and the alkaline solution is preferably a 13 wt% aqueous solution of sodium hydroxide.

[0037] In this invention, with hydroxyethyl cellulose as 1 part, the amount of isopropanol in step (1) is 6-8 parts, for example 6.5 parts, 7 parts, 7.5 parts, etc., the amount of 3-chloro-2-hydroxypropyltrimethylammonium chloride is 0.8-1.1 parts, for example 0.9 parts, 1 part, 1.05 parts, etc., and the amount of alkali solution is 1.3-1.7 parts, for example 1.4 parts, 1.5 parts, 1.6 parts, etc.

[0038] In this invention, the amount of acetic acid used in step (2) is 0.05-0.07 parts, for example 0.06 parts, based on 1 part of hydroxyethyl cellulose.

[0039] In this invention, the amount of the 80% isopropanol aqueous solution used in step (3) is 8-10 parts, for example 9 parts.

[0040] In this invention, the product described in step (3) is a high-nitrogen polyquaternary ammonium salt-10, with a nitrogen content of 1.5-2.2 wt%, a sodium ion content of <1 wt%, and a free chloride ion content of <5.5 wt%.

[0041] The present invention will be further described below with reference to specific embodiments. These embodiments are only for illustrating the present invention, but the implementation of the invention is not limited thereto.

[0042] In the examples and comparative examples, conductivity was tested using a conductivity meter. The filtrate after washing was used for measurement. The washing endpoint was determined based on the conductivity of the filtrate when the product was clean (300-350 μS / cm). At this point, the clean product should have a sodium ion content of <1% and a free chloride ion content of 4.4%-5.5%.

[0043] For tests on sodium ions (NF T90-048-1999) and chloride ions (GB 11897-1989) in the product, the product must be dissolved in water to prepare a 2% (w / w) aqueous solution for testing.

[0044] The nitrogen content (mass percentage) in the product was determined in accordance with GB / T 22427.10-2008.

[0045] Example 1

[0046] Using 1 part hydroxyethyl cellulose, 6 parts isopropanol were added under normal temperature, pressure, and an inert gas environment. While stirring, 0.8 parts 3-chloro-2-hydroxypropyltrimethylammonium chloride etherifying agent and 1.3 parts 15 wt% sodium hydroxide aqueous solution were added simultaneously and uniformly. After stirring for 10 minutes, white granular sodium chloride solid gradually formed in the reaction system. The white solid was filtered, and the reaction solution was retained. 1 part hydroxyethyl cellulose was added to the reaction solution, and the reaction was carried out at 40℃ for 6 hours. After the reaction was completed, 0.05 parts acetic acid was added to stop the reaction. The resulting substance was filtered, washed twice with 8 parts 80% isopropanol aqueous solution, and filtered again. The conductivity of the washed filtrate was measured to be 343 μS / cm using a conductivity meter. The filtered substance was dried and pulverized to obtain a polyquaternium-10 product with a sodium ion content of 0.7%, a free chloride ion content of 4.8%, and a nitrogen content of 1.8%.

[0047] Example 2

[0048] Using 1 part hydroxyethyl cellulose, 8 parts isopropanol were added under normal temperature and pressure and in an inert gas environment. While stirring, 1.1 parts 3-chloro-2-hydroxypropyltrimethylammonium chloride etherifying agent and 1.7 parts 15wt% sodium hydroxide aqueous solution were added simultaneously and evenly. After stirring for 15 minutes, white granular sodium chloride solid gradually formed in the reaction system. The white solid was filtered, and the reaction solution was retained. 1 part hydroxyethyl cellulose was added to the reaction solution, and the reaction was carried out at 60℃ for 4 hours. After the reaction was completed, 0.07 parts acetic acid was added to stop the reaction. The resulting substance was filtered, washed with 10 parts 80% isopropanol aqueous solution, and filtered three times. When the conductivity of the washed filtrate was measured to be 305 μS / cm using a conductivity meter, the filtered substance was dried and pulverized to obtain a polyquaternium-10 product with a sodium ion content of 0.7%, a free chloride ion content of 4.5%, and a nitrogen content of 1.9%.

[0049] Example 3

[0050] Using 1 part hydroxyethyl cellulose, 8 parts isopropanol were added under normal temperature and pressure and in an inert gas environment. While stirring, 1.1 parts 3-chloro-2-hydroxypropyltrimethylammonium chloride etherifying agent and 1.7 parts 15wt% sodium hydroxide aqueous solution were added simultaneously and evenly. After stirring for 15 minutes, white granular sodium chloride solid gradually formed in the reaction system. The white solid was filtered, and the reaction solution was retained. 1 part hydroxyethyl cellulose was added to the reaction solution, and the reaction was carried out at 60℃ for 4 hours. After the reaction was completed, 0.07 parts acetic acid was added to stop the reaction. The resulting substance was filtered, washed with 5 parts 80% isopropanol aqueous solution, and filtered three times. When the conductivity of the washed filtrate was measured to be 340 μS / cm using a conductivity meter, the filtered substance was dried and pulverized to obtain a polyquaternium-10 product with a sodium ion content of 0.7%, a free chloride ion content of 4.7%, and a total content of 1.9%.

[0051] Example 4

[0052] Using 1 part hydroxyethyl cellulose, 8 parts isopropanol were added under normal temperature, pressure, and an inert gas environment. While stirring, 1.1 parts 3-chloro-2-hydroxypropyltrimethylammonium chloride etherifying agent and 1.7 parts 15 wt% sodium hydroxide aqueous solution were added simultaneously and evenly. After stirring for 15 minutes, white granular sodium chloride solid gradually formed in the reaction system. The white solid was filtered, and the reaction solution was retained. 1 part hydroxyethyl cellulose was added to the reaction solution, and the reaction was carried out at 60℃ for 4 hours. After the reaction was completed, 0.07 parts acetic acid was added to stop the reaction. The resulting substance was filtered, washed with 5 parts 80% isopropanol aqueous solution, and filtered 5 times. When the conductivity of the washed filtrate was measured to be 346 μS / cm using a conductivity meter, the filtered substance was dried and pulverized to obtain a polyquaternium-10 product with a sodium ion content of 0.8%, a free chloride ion content of 4.7%, and a total content of 1.9%.

[0053] Comparative Example 1

[0054] One part of hydroxyethyl cellulose was used, and six parts of isopropanol were added under normal temperature, pressure, and an inert gas environment. One part of hydroxyethyl cellulose was added under stirring, followed by 1.3 parts of 15 wt% sodium hydroxide aqueous solution and 0.8 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride etherifying agent. The mixture was stirred and reacted at 40°C for 6 hours. After the reaction was completed, 0.05 parts of acetic acid were added to stop the reaction. The resulting substance was filtered, washed twice with 8 parts of 80% isopropanol aqueous solution, and the conductivity of the filtrate was measured to be 830 μS / cm. The filtered substance was dried and pulverized to obtain a polyquaternium-10 product with a sodium ion content of 2.3%, a free chloride ion content of 9.5%, and a content of 1.8%.

[0055] Comparative Example 2

[0056] One part of hydroxyethyl cellulose was used, and eight parts of isopropanol were added under normal temperature, pressure, and an inert gas environment. One part of hydroxyethyl cellulose was added under stirring, followed by 1.7 parts of 15 wt% sodium hydroxide aqueous solution and 1.1 parts of 3-chloro-2-hydroxypropyltrimethylammonium chloride etherifying agent. The mixture was stirred and reacted at 60°C for 4 hours. After the reaction was completed, 0.07 parts of acetic acid were added to stop the reaction. The resulting substance was filtered and washed three times with 10 parts of 80% isopropanol aqueous solution using conventional washing methods. The conductivity of the filtrate was measured to be 721 μS / cm using a conductivity meter. The filtered substance was dried and pulverized to obtain a 1.9% polyquaternium-10 product with a sodium ion content of 1.9% and a free chloride ion content of 9.0%.

[0057] In summary, as shown in Examples 1-2 and Comparative Examples 1-2, when using the desalination method to produce polyquaternary ammonium salt-10, the number of washes required is significantly less than that required for products produced without the desalination method. This means that the crude product produced has significantly fewer impurity salts. This process can significantly reduce the consumption of washing solvents and post-processing time, thereby reducing production costs. Furthermore, as demonstrated in Examples 1 and Comparative Example 1, this process can reliably pinpoint the washing endpoint during post-processing washing using the conductivity method. The method is simple and reliable, and the washing endpoint can be directly determined using conductivity values, effectively improving production efficiency.

Claims

1. A method for producing polyquaternium-10, characterized in that, Includes the following steps: (1) Desalination: Isopropanol is added to the reactor under an inert gas environment. Cationic etherifying agent and a small excess of alkaline solution are added under stirring. Stirring is continued until white granular sodium chloride solid is gradually produced in the reaction system. The white solid is filtered and the reaction solution is retained. (2) Add hydroxyethyl cellulose to the reaction solution of step (1) and carry out the reaction. After the reaction is completed, add a terminator to stop the reaction. (3) Filter the reaction product obtained in step (2), wash and filter repeatedly, and use a conductivity meter to monitor the conductivity of the filtrate after washing. When the conductivity reaches 300-350µS / cm, it is the washing endpoint. Dry and pulverize the filtered substance to obtain polyquaternium-10 product. Based on the amount of hydroxyethyl cellulose used in step (2) being 1 part, the amount of solvent used in step (1) is 6-8 parts, the amount of cationic etherifying agent is 0.8-1.1 parts, the amount of alkali solution is 1.3-1.7 parts, and the mass concentration of alkali solution is 10-30 wt%; The cationic etherifying agent is at least one of 3-chloro-2-hydroxypropyltrimethylammonium chloride and glycidyltrimethylammonium chloride.

2. The method according to claim 1, characterized in that, The terminator is an acid-based terminator.

3. The method according to claim 2, characterized in that, The cationic etherifying agent is 3-chloro-2-hydroxypropyltrimethylammonium chloride; and / or The terminating agent is acetic acid.

4. The method according to claim 2, characterized in that, The 3-chloro-2-hydroxypropyltrimethylammonium chloride is an aqueous solution with a mass concentration of 1-69 wt%; and / or The alkaline solution is any one of an aqueous solution of sodium hydroxide, potassium hydroxide, or ammonia.

5. The method according to claim 4, characterized in that, The 3-chloro-2-hydroxypropyltrimethylammonium chloride is an aqueous solution with a mass concentration of 69 wt%; and / or The mass concentration of the alkaline solution is 13 wt%.

6. The method according to any one of claims 1-5, characterized in that, Step (1) is carried out at room temperature and pressure.

7. The method according to claim 1, characterized in that, The reaction described in step (2) is carried out at a temperature of 40-60°C for 4-6 hours.

8. The method according to claim 1, characterized in that, The amount of the terminator in step (2) is 0.05-0.07 parts, which is based on 1 part of hydroxyethyl cellulose.

9. The method according to claim 1, characterized in that, The washing step (3) uses an isopropanol aqueous solution with a mass concentration of 80 wt%.

10. The method according to claim 9, characterized in that, The amount of the 80wt% isopropanol aqueous solution used is 8-10 parts, with 1 part being hydroxyethyl cellulose.