Cationic etherifying agent and preparation method thereof

Abstract

The invention relates to the technical field of etherifying agents, and discloses a cationic etherifying agent and a preparation method thereof. The invention obtains a cationic etherifying agent by adding guanidine quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and glycidyl triethylammonium chloride into a reactor and stirring. The polyhexamethylene biguanide in the guanidine quaternary ammonium salt electrostatically adsorbs with the anion site on the surface of bacterial cells, denatures or destroys the cell structure, and plays a bactericidal role; the quaternary ammonium salt is adsorbed onto the surface of the bacteria, and the hydrophobic group is inserted into the lipid layer, so that the intracellular substances leak out, resulting in bacterial death; the guanidine group and the quaternary ammonium salt play a synergistic effect, and play a stronger bactericidal role; in the quaternary phosphonium salt polyacrylamide, the quaternary phosphonium salt carries a positive charge, can be adsorbed onto the bacterial cell wall and penetrate the cell membrane, reacts with the lipid or protein of the cell membrane, lyses the cell wall, and causes bacterial death; the quaternary phosphonium salt is grafted into chitosan and polyacrylamide, and the positive charge density is increased, thereby enhancing the antibacterial effect.

Description

Technical Field

[0001] The invention relates to the technical field of etherifying agents, in particular to a cationic etherifying agent and a preparation method thereof. Background Art

[0002] Etherifying agents are a class of chemical substances that can promote the formation of ether compounds. They usually contain active groups, such as hydroxyl or halogenated hydrocarbon groups, which can react with other molecules to form ether bonds. Cationic etherifying agents refer to compounds that can introduce cationic groups in chemical reactions. They are widely used in the fields of chemistry and biochemistry. They are usually used as catalysts, surfactants, lubricants, and stabilizers for polymerization reactions. However, the antibacterial effect of commonly used cationic etherifying agents is poor, which limits their application in more fields. For example, patent CN111978186A discloses a method for preparing a solid cationic etherifying agent. By selecting solvents, controlling pH value and temperature, the production process is made more environmentally friendly and efficient, and the product yield is improved, but its antibacterial effect needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides a cationic etherifying agent and a preparation method thereof, which have good antibacterial effects.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical solution: a cationic etherifying agent, comprising the following weight components: 15-20 weight parts of guanidine quaternary ammonium salt, 16-18 weight parts of quaternary phosphonium salt polyacrylamide, and 10-14 weight parts of glycidyl triethylammonium chloride.

[0007] Preferably, the preparation method of the guanidine quaternary ammonium salt comprises the following steps:

[0008] (1) Add tetramethylammonium chloride and deionized water to a round-bottom flask, stir at 8-12°C for 40-60 minutes to fully dissolve the tetramethylammonium chloride, dropwise add epichlorohydrin to the tetramethylammonium chloride solution, heat to 20-25°C and keep the temperature for 1.5-2 hours, then heat to 32-35°C and continue to react for 3-3.5 hours. After the reaction is completed, cool and distill at normal pressure to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride;

[0009] (2) adding 7-9 parts by weight of cyanuric chloride to N,N-dimethylformamide solvent at 0-5°C, stirring to dissolve, and then dropping 12-14 parts by weight of polyhexamethylene biguanide solution therein, adjusting the reaction pH to neutral with 0.3-0.5 parts by weight of an acid binding agent, and reacting at a constant temperature for 7-8 hours. After the reaction is completed, washing and drying to obtain intermediate 1;

[0010] (3) 3-chloro-2-hydroxypropyltrimethylammonium chloride is fully dissolved in deionized water, and intermediate 1 is added thereto. The reaction is carried out at 40-50° C. for 12-14 h. After the reaction is completed, the mixture is dialyzed and freeze-dried to obtain a guanidine quaternary ammonium salt.

[0011] Preferably, in step (1), the mass ratio of tetramethylammonium chloride to epichlorohydrin is 1:1.1-1.15.

[0012] Preferably, the acid binding agent in step (2) is triethylamine.

[0013] Preferably, in step (3), the mass ratio of 3-chloro-2-hydroxypropyltrimethylammonium chloride to intermediate 1 is 1:0.8-0.9.

[0014] Preferably, the preparation method of the quaternary phosphonium salt polyacrylamide comprises the following steps:

[0015] S1. Dissolve 11-13 parts by weight of chitosan in an acetic acid solution, stir to dissolve, add 0.2-0.5 parts by weight of 1-hydroxybenzotriazole initiator, stir for 25-30min, then add 12-14 parts by weight of 6-carboxyhexyltriphenylphosphonium bromide, pass nitrogen protection, react at 72-78 ° C for 18-20h, after the reaction is completed, filter, freeze-dry to obtain quaternary phosphonium salt modified chitosan;

[0016] S2. Add 3-acryloxypropylmethyldichlorosilane and quaternary phosphonium salt-modified chitosan to deionized water, stir and mix, react at 42-45 ° C for 2.5-3.5h, and after the reaction, wash and dry to obtain intermediate 2;

[0017] S3. 13-15 parts by weight of acrylamide, 10-12 parts by weight of intermediate 2, 2-4 parts by weight of disodium ethylenediaminetetraacetate and deionized water are mixed to form an aqueous phase, 6-9 parts by weight of liquid paraffin and 9-11 parts by weight of an emulsifier are mixed to form an oil phase, the oil phase is added to a flask and nitrogen is introduced for protection, the aqueous phase solution is added dropwise thereto, the mixture is stirred at a speed of 300-400 rpm, and 0.4-0.6 parts by weight of an initiator is added dropwise thereto, after the addition is complete, the mixture is heated to 50-60°C and kept for reaction for 3-5 hours, after the reaction is completed, the mixture is cooled and dried to obtain quaternary phosphonium salt polyacrylamide.

[0018] Preferably, the mass fraction of the acetic acid solution in S1 is 1-1.5%.

[0019] Preferably, the mass ratio of 3-acryloxypropylmethyldichlorosilane to quaternary phosphonium salt modified chitosan in S2 is 1:0.45-0.5.

[0020] Preferably, the emulsifier in S3 is sorbitan trioleate, and the initiator is sodium bisulfite.

[0021] Preferably, the preparation method of the cationic etherifying agent is: adding guanidine quaternary ammonium salt, quaternary phosphonium salt polyacrylamide, and epoxypropyl triethylammonium chloride into a reactor, stirring at a speed of 600-800 rpm for 8-12 minutes to obtain the cationic etherifying agent.

[0022] 3. Beneficial technical effects

[0023] The invention obtains the cationic etherifying agent by adding guanidine quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and epoxypropyl triethylammonium chloride into a reactor and stirring.

[0024] The quaternary ammonium salt group in tetramethylammonium chloride attacks the epoxy group in epichlorohydrin to undergo a ring-opening reaction to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride. A chlorine atom in cyanuric chloride undergoes a substitution reaction with the amino group in polyhexamethylene biguanide to introduce a guanidine group to obtain intermediate 1. The second chlorine atom in intermediate 1 undergoes a substitution reaction with the hydroxyl group in 3-chloro-2-hydroxypropyltrimethylammonium chloride to obtain a guanidine quaternary ammonium salt. The amino group in chitosan reacts with the carboxyl group in 6-carboxyhexyltriphenylphosphonium bromide to obtain quaternary phosphonium salt-modified chitosan and introduce a hydroxyl group. The chlorine atom in 3-acryloxypropylmethyldichlorosilane undergoes a substitution reaction with the hydroxyl group in quaternary phosphonium salt-modified chitosan to obtain intermediate 2 and introduce an olefin group. Using the reverse emulsion polymerization method, acrylamide and intermediate 2 undergo a polymerization reaction to obtain quaternary phosphonium salt polyacrylamide.

[0025] The bactericidal mechanism of polyhexamethylene biguanide in guanidine quaternary ammonium salts is mainly based on its high activity, which makes the polymer positively charged and easily electrostatically adsorbed to the anionic sites on the surface of bacterial cells, causing the cell surface structure to denature or destroy, thereby playing a bactericidal role; quaternary ammonium salts adsorb to the surface of bacteria, and the hydrophobic groups are inserted into the lipid layer, which changes the permeability of the cell membrane, destroys the membrane structure, causes the leakage of intracellular substances, and leads to bacterial death; the guanidine group and the quaternary ammonium salt play a synergistic effect and play a stronger bactericidal role; in quaternary phosphonium salt polyacrylamide, the quaternary phosphonium salt carries a positive charge and can adsorb to the bacterial cell wall and penetrate the cell membrane, reacting with the lipids or proteins of the cell membrane, causing the cell membrane structure to be disordered and components to leak, causing the cell wall to lyse and the cell structure to lose direction, ultimately leading to bacterial death, and the quaternary phosphonium salt is grafted into chitosan and polyacrylamide to increase the positive charge density, thereby enhancing the antibacterial effect. DETAILED DESCRIPTION Example 1

[0026] (1) Add tetramethylammonium chloride and deionized water to a round-bottom flask, stir at 8°C for 40 minutes to fully dissolve the tetramethylammonium chloride, dropwise add epichlorohydrin to the tetramethylammonium chloride solution, wherein the mass ratio of tetramethylammonium chloride to epichlorohydrin is 1:1.1, heat to 20°C and keep the temperature for 1.5 hours, then heat to 32°C and continue the reaction for 3 hours. After the reaction is completed, cool and distill at normal pressure to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride;

[0027] (2) adding 7 parts by weight of cyanuric chloride to N,N-dimethylformamide solvent at 0°C, stirring to dissolve, and then dropping 12 parts by weight of polyhexamethylene biguanide solution thereinto, adjusting the reaction pH to neutral with 0.3 parts by weight of an acid binder, wherein the acid binder is triethylamine, and reacting at a constant temperature for 7 hours. After the reaction is completed, washing and drying are performed to obtain intermediate 1;

[0028] (3) 3-chloro-2-hydroxypropyltrimethylammonium chloride was fully dissolved in deionized water, and intermediate 1 was added thereto, wherein the mass ratio of 3-chloro-2-hydroxypropyltrimethylammonium chloride to intermediate 1 was 1:0.8, and the mixture was reacted at 40° C. for 12 h. After the reaction was completed, the mixture was dialyzed and freeze-dried to obtain a guanidine quaternary ammonium salt;

[0029] (4) Dissolve 11 parts by weight of chitosan in acetic acid solution, wherein the mass fraction of the acetic acid solution is 1%, stir to dissolve, add 0.2 parts by weight of 1-hydroxybenzotriazole initiator, stir for 25 minutes, then add 12 parts by weight of 6-carboxyhexyltriphenylphosphonium bromide, pass nitrogen protection, react at 72°C for 18 hours, filter after the reaction, and freeze-dry to obtain quaternary phosphonium salt modified chitosan;

[0030] (5) adding 3-acryloxypropylmethyldichlorosilane and quaternary phosphonium salt-modified chitosan to deionized water, wherein the mass ratio of 3-acryloxypropylmethyldichlorosilane to quaternary phosphonium salt-modified chitosan is 1:0.45, stirring and mixing, reacting at 42° C. for 2.5 h, and after the reaction is completed, washing and drying to obtain intermediate 2;

[0031] (6) 13 parts by weight of acrylamide, 10 parts by weight of intermediate 2, 2 parts by weight of disodium ethylenediaminetetraacetate and deionized water are mixed to form an aqueous phase, 6 parts by weight of liquid paraffin and 9 parts by weight of an emulsifier are mixed, wherein the emulsifier is sorbitan trioleate, to form an oil phase, the oil phase is added to a flask and nitrogen is introduced for protection, the aqueous phase solution is added dropwise thereto, the mixture is stirred at a speed of 300 rpm, and 0.4 parts by weight of an initiator is added dropwise thereto, wherein the initiator is sodium bisulfite, after the addition is completed, the temperature is raised to 50° C. and the reaction is kept at this temperature for 3 hours, after the reaction is completed, the mixture is cooled and dried to obtain quaternary phosphonium salt polyacrylamide;

[0032] (7) 15 parts by weight of guanidine quaternary ammonium salt, 16 parts by weight of quaternary phosphonium salt polyacrylamide, and 10 parts by weight of epoxypropyl triethylammonium chloride were added to a reactor and stirred at 600 rpm for 8 minutes to obtain a cationic etherifying agent. Example 2

[0033] (1) Add tetramethylammonium chloride and deionized water to a round-bottom flask, stir at 12°C for 60 minutes to fully dissolve the tetramethylammonium chloride, dropwise add epichlorohydrin to the tetramethylammonium chloride solution, wherein the mass ratio of tetramethylammonium chloride to epichlorohydrin is 1:1.15, heat to 25°C and keep the temperature for 2 hours, then heat to 35°C and continue the reaction for 3.5 hours. After the reaction is completed, cool and distill at normal pressure to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride;

[0034] (2) Add 9 parts by weight of cyanuric chloride to N,N-dimethylformamide solvent at 5°C, stir to dissolve, then add 14 parts by weight of polyhexamethylene biguanide solution dropwise thereto, adjust the reaction pH to neutral with 0.5 parts by weight of an acid binder, wherein the acid binder is triethylamine, and react at a constant temperature for 8 hours. After the reaction is completed, wash and dry to obtain intermediate 1;

[0035] (3) 3-chloro-2-hydroxypropyltrimethylammonium chloride was fully dissolved in deionized water, and intermediate 1 was added thereto, wherein the mass ratio of 3-chloro-2-hydroxypropyltrimethylammonium chloride to intermediate 1 was 1:0.9, and the mixture was reacted at 50° C. for 14 h. After the reaction was completed, the mixture was dialyzed and freeze-dried to obtain a guanidine quaternary ammonium salt;

[0036] (4) Dissolve 13 parts by weight of chitosan in acetic acid solution, wherein the mass fraction of the acetic acid solution is 1.5%, stir to dissolve, add 0.5 parts by weight of 1-hydroxybenzotriazole initiator, stir for 30 minutes, then add 14 parts by weight of 6-carboxyhexyltriphenylphosphonium bromide, pass nitrogen protection, react at 78°C for 20 hours, filter after the reaction, and freeze-dry to obtain quaternary phosphonium salt modified chitosan;

[0037] (5) adding 3-acryloxypropylmethyldichlorosilane and quaternary phosphonium salt-modified chitosan to deionized water, wherein the mass ratio of 3-acryloxypropylmethyldichlorosilane to quaternary phosphonium salt-modified chitosan is 1:0.5, stirring and mixing, reacting at 45° C. for 3.5 h, and after the reaction is completed, washing and drying to obtain intermediate 2;

[0038] (6) 15 parts by weight of acrylamide, 12 parts by weight of intermediate 2, 4 parts by weight of disodium ethylenediaminetetraacetate and deionized water are mixed to form an aqueous phase, 9 parts by weight of liquid paraffin and 11 parts by weight of an emulsifier, wherein the emulsifier is sorbitan trioleate, are mixed to form an oil phase, the oil phase is added to a flask and nitrogen is introduced for protection, the aqueous phase solution is added dropwise thereto, the mixture is stirred at a speed of 400 rpm, and 0.6 parts by weight of an initiator, wherein the initiator is sodium bisulfite, is added dropwise thereto, and after the addition is complete, the mixture is heated to 60° C. and kept for reaction for 5 hours. After the reaction is completed, the mixture is cooled and dried to obtain quaternary phosphonium salt polyacrylamide;

[0039] (7) 20 parts by weight of guanidine quaternary ammonium salt, 18 parts by weight of quaternary phosphonium salt polyacrylamide, and 14 parts by weight of epoxypropyl triethylammonium chloride were added to a reactor and stirred at 800 rpm for 12 minutes to obtain a cationic etherifying agent. Example 3

[0040] (1) Add tetramethylammonium chloride and deionized water to a round-bottom flask, stir at 10°C for 50 minutes to fully dissolve the tetramethylammonium chloride, add epichlorohydrin dropwise to the tetramethylammonium chloride solution, wherein the mass ratio of tetramethylammonium chloride to epichlorohydrin is 1:1.12, heat to 23°C and keep the temperature for 1.8 hours, then heat to 33°C and continue the reaction for 3.2 hours. After the reaction is completed, cool and distill at normal pressure to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride;

[0041] (2) Add 8 parts by weight of cyanuric chloride to N,N-dimethylformamide solvent at 2°C, stir to dissolve, then add 13 parts by weight of polyhexamethylene biguanide solution dropwise thereto, adjust the reaction pH to neutral with 0.4 parts by weight of an acid binder, wherein the acid binder is triethylamine, react at a constant temperature for 7.5 hours, and after the reaction is completed, wash and dry to obtain intermediate 1;

[0042] (3) 3-chloro-2-hydroxypropyltrimethylammonium chloride was fully dissolved in deionized water, and intermediate 1 was added thereto, wherein the mass ratio of 3-chloro-2-hydroxypropyltrimethylammonium chloride to intermediate 1 was 1:0.85, and the mixture was reacted at 45° C. for 13 h. After the reaction was completed, the mixture was dialyzed and freeze-dried to obtain a guanidine quaternary ammonium salt;

[0043] (4) Dissolve 12 parts by weight of chitosan in acetic acid solution, wherein the mass fraction of the acetic acid solution is 1.2%, stir to dissolve, add 0.3 parts by weight of 1-hydroxybenzotriazole initiator, stir for 28 minutes, then add 13 parts by weight of 6-carboxyhexyltriphenylphosphonium bromide, pass nitrogen protection, react at 75°C for 19 hours, filter after the reaction, and freeze-dry to obtain quaternary phosphonium salt modified chitosan;

[0044] (5) adding 3-acryloxypropylmethyldichlorosilane and quaternary phosphonium salt-modified chitosan to deionized water, wherein the mass ratio of 3-acryloxypropylmethyldichlorosilane to quaternary phosphonium salt-modified chitosan is 1:0.48, stirring and mixing, reacting at 43° C. for 3 h, and after the reaction is completed, washing and drying to obtain intermediate 2;

[0045] (6) 14 parts by weight of acrylamide, 11 parts by weight of intermediate 2, 3 parts by weight of disodium ethylenediaminetetraacetate and deionized water are mixed to form an aqueous phase, 8 parts by weight of liquid paraffin and 10 parts by weight of an emulsifier are mixed, wherein the emulsifier is sorbitan trioleate, to form an oil phase, the oil phase is added to a flask and nitrogen is introduced for protection, the aqueous phase solution is added dropwise thereto, the mixture is stirred at a speed of 350 rpm, and 0.5 parts by weight of an initiator is added dropwise thereto, wherein the initiator is sodium bisulfite, after the addition is completed, the temperature is raised to 55° C. and the reaction is maintained for 4 hours, after the reaction is completed, the mixture is cooled and dried to obtain quaternary phosphonium salt polyacrylamide;

[0046] (7) 18 parts by weight of guanidine quaternary ammonium salt, 17 parts by weight of quaternary phosphonium salt polyacrylamide, and 12 parts by weight of epoxypropyl triethylammonium chloride were added to a reactor and stirred at 700 rpm for 10 minutes to obtain a cationic etherifying agent. Example 4

[0047] (1) Add tetramethylammonium chloride and deionized water to a round-bottom flask, stir at 8°C for 40 minutes to fully dissolve the tetramethylammonium chloride, dropwise add epichlorohydrin to the tetramethylammonium chloride solution, wherein the mass ratio of tetramethylammonium chloride to epichlorohydrin is 1:1.1, heat to 20°C and keep the temperature for 1.5 hours, then heat to 32°C and continue the reaction for 3 hours. After the reaction is completed, cool and distill at normal pressure to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride;

[0048] (2) adding 7 parts by weight of cyanuric chloride to N,N-dimethylformamide solvent at 0°C, stirring to dissolve, and then dropping 12 parts by weight of polyhexamethylene biguanide solution thereinto, adjusting the reaction pH to neutral with 0.3 parts by weight of an acid binder, wherein the acid binder is triethylamine, and reacting at a constant temperature for 7 hours. After the reaction is completed, washing and drying are performed to obtain intermediate 1;

[0049] (3) 3-chloro-2-hydroxypropyltrimethylammonium chloride was fully dissolved in deionized water, and intermediate 1 was added thereto, wherein the mass ratio of 3-chloro-2-hydroxypropyltrimethylammonium chloride to intermediate 1 was 1:0.9, and the mixture was reacted at 50° C. for 14 h. After the reaction was completed, the mixture was dialyzed and freeze-dried to obtain a guanidine quaternary ammonium salt;

[0050] (4) Dissolve 13 parts by weight of chitosan in acetic acid solution, wherein the mass fraction of the acetic acid solution is 1.5%, stir to dissolve, add 0.5 parts by weight of 1-hydroxybenzotriazole initiator, stir for 30 minutes, then add 14 parts by weight of 6-carboxyhexyltriphenylphosphonium bromide, pass nitrogen protection, react at 78°C for 20 hours, filter after the reaction, and freeze-dry to obtain quaternary phosphonium salt modified chitosan;

[0051] (5) adding 3-acryloxypropylmethyldichlorosilane and quaternary phosphonium salt-modified chitosan to deionized water, wherein the mass ratio of 3-acryloxypropylmethyldichlorosilane to quaternary phosphonium salt-modified chitosan is 1:0.48, stirring and mixing, reacting at 43° C. for 3 h, and after the reaction is completed, washing and drying to obtain intermediate 2;

[0052] (6) 14 parts by weight of acrylamide, 11 parts by weight of intermediate 2, 3 parts by weight of disodium ethylenediaminetetraacetate and deionized water are mixed to form an aqueous phase, 8 parts by weight of liquid paraffin and 10 parts by weight of an emulsifier are mixed, wherein the emulsifier is sorbitan trioleate, to form an oil phase, the oil phase is added to a flask and nitrogen is introduced for protection, the aqueous phase solution is added dropwise thereto, the mixture is stirred at a speed of 350 rpm, and 0.5 parts by weight of an initiator is added dropwise thereto, wherein the initiator is sodium bisulfite, after the addition is completed, the temperature is raised to 55° C. and the reaction is maintained for 4 hours, after the reaction is completed, the mixture is cooled and dried to obtain quaternary phosphonium salt polyacrylamide;

[0053] (7) 18 parts by weight of guanidine quaternary ammonium salt, 17 parts by weight of quaternary phosphonium salt polyacrylamide, and 12 parts by weight of epoxypropyl triethylammonium chloride were added to a reactor and stirred at 700 rpm for 10 minutes to obtain a cationic etherifying agent.

[0054] Comparative Example 1

[0055] This comparative example is compared with Example 4, except that no guanidine quaternary ammonium salt is added.

[0056] Comparative Example 2

[0057] This comparative example is compared with Example 4, except that no quaternary phosphonium salt polyacrylamide is added.

[0058] With Staphylococcus aureus, Escherichia coli, and Candida albicans as the test bacteria, a bacterial suspension with a concentration of 1×105 CFU / mL was prepared, 1.2 mL of the bacterial suspension was transferred to a sterilized culture dish containing MH broth medium, and then the solid cationic etherification agent sample was attached to the surface of the culture medium, and cultured at 42°C for 15 hours in a constant temperature incubator, and the diameter of the inhibition zone was measured after culture. The test results are shown in Table 1.

[0059] Table 1: Antimicrobial testing.

[0060]

[0061] It can be seen from Table 1 that Examples 1-4 of the present invention have better antibacterial effects than Comparative Examples 1-2.

[0062] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A cationic etherifying agent, characterized in that: The invention comprises the following components by weight: 15-20 parts by weight of guanidine quaternary ammonium salt, 16-18 parts by weight of quaternary phosphonium salt polyacrylamide, and 10-14 parts by weight of glycidyl triethylammonium chloride; The preparation method of the guanidine quaternary ammonium salt comprises the following steps: (1) Add tetramethylammonium chloride and deionized water to a round-bottom flask, stir at 8-12°C for 40-60 minutes to fully dissolve the tetramethylammonium chloride, dropwise add epichlorohydrin to the tetramethylammonium chloride solution, heat to 20-25°C and keep the temperature for 1.5-2 hours, then heat to 32-35°C and continue to react for 3-3.5 hours. After the reaction is completed, cool and distill at normal pressure to obtain 3-chloro-2-hydroxypropyltrimethylammonium chloride; (2) adding 7-9 parts by weight of cyanuric chloride to N,N-dimethylformamide solvent at 0-5°C, stirring to dissolve, and then dropping 12-14 parts by weight of polyhexamethylene biguanide solution therein, adjusting the reaction pH to neutral with 0.3-0.5 parts by weight of an acid binding agent, and reacting at a constant temperature for 7-8 hours. After the reaction is completed, washing and drying to obtain intermediate 1; (3) 3-chloro-2-hydroxypropyltrimethylammonium chloride is fully dissolved in deionized water, and intermediate 1 is added thereto. The reaction is carried out at 40-50° C. for 12-14 hours. After the reaction is completed, the mixture is dialyzed and freeze-dried to obtain a guanidine quaternary ammonium salt; The preparation method of the quaternary phosphonium salt polyacrylamide comprises the following steps: S1. Dissolve 11-13 parts by weight of chitosan in an acetic acid solution, stir to dissolve, add 0.2-0.5 parts by weight of 1-hydroxybenzotriazole initiator, stir for 25-30min, then add 12-14 parts by weight of 6-carboxyhexyltriphenylphosphonium bromide, pass nitrogen protection, react at 72-78 ° C for 18-20h, after the reaction is completed, filter, freeze-dry to obtain quaternary phosphonium salt modified chitosan; S2. Add 3-acryloxypropylmethyldichlorosilane and quaternary phosphonium salt-modified chitosan to deionized water, stir and mix, react at 42-45 ° C for 2.5-3.5h, and after the reaction, wash and dry to obtain intermediate 2; S3. 13-15 parts by weight of acrylamide, 10-12 parts by weight of intermediate 2, 2-4 parts by weight of disodium ethylenediaminetetraacetate and deionized water are mixed to form an aqueous phase, 6-9 parts by weight of liquid paraffin and 9-11 parts by weight of an emulsifier are mixed to form an oil phase, the oil phase is added to a flask and nitrogen is introduced for protection, the aqueous phase solution is added dropwise thereto, the mixture is stirred at a speed of 300-400 rpm, and 0.4-0.6 parts by weight of an initiator is added dropwise thereto, after the addition is complete, the mixture is heated to 50-60°C and kept for reaction for 3-5 hours, after the reaction is completed, the mixture is cooled and dried to obtain quaternary phosphonium salt polyacrylamide.

2. The cationic etherifying agent according to claim 1, characterized in that In the step (1), the mass ratio of tetramethylammonium chloride to epichlorohydrin is 1:1.1-1.

15.

3. The cationic etherifying agent according to claim 1, characterized in that The acid binding agent in step (2) is triethylamine.

4. The cationic etherifying agent according to claim 1, characterized in that In the step (3), the mass ratio of 3-chloro-2-hydroxypropyltrimethylammonium chloride to intermediate 1 is 1:0.8-0.

9.

5. The cationic etherifying agent according to claim 1, characterized in that The mass fraction of the acetic acid solution in S1 is 1-1.5%.

6. The cationic etherifying agent according to claim 1, characterized in that The mass ratio of 3-acryloxypropylmethyldichlorosilane to quaternary phosphonium salt modified chitosan in S2 is 1:0.45-0.

5.

7. The cationic etherifying agent according to claim 1, characterized in that The emulsifier in S3 is sorbitan trioleate, and the initiator is sodium bisulfite.

8. A method for preparing a cationic etherifying agent according to any one of claims 1 to 7, characterized in that: The preparation method of the cationic etherifying agent is as follows: adding guanidine quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and epoxypropyl triethylammonium chloride into a reactor, stirring at a speed of 600-800 rpm for 8-12 minutes, and obtaining the cationic etherifying agent.

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