Preparation method of a long-acting adsorption type odor and antibacterial agent

Abstract

The present invention discloses a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, which relates to the technical field of antibacterial agent preparation. The preparation steps are as follows: First, 1,4-benzenediacetic acid, methyl terephthalate, polyvinyl alcohol and an antibacterial monomer are placed in deionized water and stirred to obtain a mixed material liquid; Second, the mixed material liquid is pre-polymerized to obtain a pre-polymerized material liquid; Third, an adsorption type antibacterial particle is added to the pre-polymerized material liquid, and a cross-linking agent is added, and the mixture is stirred and heated to polymerize until the material liquid becomes thick to obtain a thick material; Fourth, the thick material is dried in an oven, and after grinding, a long-acting adsorption type odor and deodorization antibacterial agent is prepared; The antibacterial polymer layer coated on the periphery of the present invention has good antibacterial effects. At the same time, due to its coating effect, the antibacterial polymer layer can play a good slow-release role on the antibacterial agent in the adsorption type antibacterial particle. Under the action of the internal and external antibacterial effects, the antibacterial agent not only has strong antibacterial ability, but also has a long-lasting antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial agent preparation, and particularly relates to a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent. Background Art

[0002] In recent years, antibacterial agents have been increasingly used in people's daily lives and have caused waves of enthusiasm.

[0003] Antibacterial agents can be divided into natural antibacterial agents, organic antibacterial agents, and inorganic antibacterial agents. Among them, natural antibacterial agents are the first antibacterial agents used by people. Natural antibacterial agents generally come from nature and have safety guarantees. They are non-toxic and have no side effects when used. With the improvement of human environmental protection awareness, natural antibacterial agents will play a greater role. Inorganic antibacterial agents use metal ions such as silver and copper to produce bactericidal effects. They have relatively good heat resistance and are relatively convenient to process. Organic antibacterial agents destroy cells through chemical reactions, denature proteins, and affect metabolism, thereby playing a bactericidal role. They mainly include quaternary ammonium salts, biguanides, alcohols, phenols, etc. Their bactericidal effects are strong and their sources are relatively rich.

[0004] However, when the current antibacterial agents are applied, especially when applied to polymer materials, there are more or less defects in maintaining long-term effectiveness. For example, Patent CN113337012A discloses a composite antibacterial agent and an antibacterial masterbatch containing the composite antibacterial agent. It prepares a composite antibacterial agent by mixing clay, rare earth compounds, shell powder with nano-zinc oxide. When antibacterial, bacteria need to contact with zinc ions exposed on the polymer surface. However, since the zinc ions exposed on the surface are easily dissolved or worn, good antibacterial effects cannot be achieved. Summary of the Invention

[0005] The present invention is to overcome the above problems and proposes a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that the preparation steps are as follows:

[0008] First, 1,4-benzenediacetic acid, methyl terephthalate, polyvinyl alcohol, and an antibacterial monomer are placed in deionized water and stirred to obtain a mixed material liquid;

[0009] Second, the mixed material liquid is pre-polymerized to obtain a pre-polymerized material liquid;

[0010] Third, an adsorption type antibacterial particle is added to the pre-polymerized material liquid, and a cross-linking agent is added, and the mixture is stirred and heated for polymerization until the material liquid becomes thick to obtain a thick material;

[0011] 4. Place the thick material in an oven for drying, and then grind it to prepare a long-acting adsorption type deodorant and antibacterial agent.

[0012] In the present invention, first, 1,4-benzenediacetic acid, dimethyl terephthalate, polyvinyl alcohol and an antibacterial monomer are pre-polymerized to prepare a prepolymer with a block antibacterial structure. Subsequently, the adsorption type antibacterial particles are mixed with the pre-polymerization liquid, and then polymerization is carried out, so that the periphery of the adsorption type antibacterial particles can be coated with a polymer having an antibacterial effect. When in use, first, the outer coated antibacterial polymer layer has a good antibacterial effect. At the same time, due to its coating effect, the antibacterial polymer layer can play a good slow-release role on the antibacterial agent in the adsorption type antibacterial particles. Under the action of the internal and external antibacterial effects, the antibacterial agent not only has strong antibacterial ability, but also has a long-lasting antibacterial performance. And, in the present invention, pre-polymerization needs to be carried out first, because when the adsorption type antibacterial particles are added, the prepolymer can first play a certain coating role to prevent the antibacterial agent in the adsorption type antibacterial particles from being released during the preparation process, so that the finally prepared antibacterial agent has a good antibacterial effect.

[0013] Preferably, the mass parts of each component in step 1 are: 5-10 parts of 1,4-benzenediacetic acid, 1-5 parts of dimethyl terephthalate, 2-7 parts of polyvinyl alcohol, and 5-10 parts of antibacterial monomer.

[0014] Preferably, the concentration of the mixed liquid in step 1 is 3-10 wt%.

[0015] Preferably, the preparation steps of the antibacterial monomer in step 1 are:

[0016] Place 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol in an ethanol solvent, carry out a modification reaction at 50-70 °C, and then evaporate the solvent to prepare an antibacterial monomer.

[0017] In the present invention, 5,5-dimethylhydantoin can play a good antibacterial role, but it cannot be grafted. Therefore, in the present invention, 5,5-dimethylhydantoin is first subjected to a modification reaction with 2-chloropropane-1,3-diol, so that hydroxyl groups are connected to both ends of 5,5-dimethylhydantoin, and the antibacterial agent is grafted into the polymer in the form of a block by using the hydroxyl groups to react with other monomers, so as to dissolve the antibacterial agent during use, increase the antibacterial effect, and extend the antibacterial time.

[0018] Preferably, the mass ratio of 5,5-dimethylhydantoin to 2-chloropropane-1,3-diol is 2-4:1.

[0019] Preferably, the temperature of the pre-polymerization in step 2 is 40-70 °C, and the time is 1-3 h.

[0020] Preferably, the preparation steps of the adsorptive antibacterial particles in step three are as follows:

[0021] 1) Immerse the mesoporous silica with a hollow cavity in an aminopropyltriethoxysilane solution for amino modification;

[0022] 2) Immerse the amino-modified silica in a carboxymethyl cellulose solution and stir to disperse, and fill the carboxymethyl cellulose solution into the hollow cavity of the amino-modified silica;

[0023] 3) Place the silica filled with the carboxymethyl cellulose solution in an aqueous glyoxal solution for cross-linking reaction;

[0024] 4) Calcinate the silica after the cross-linking reaction to obtain adsorptive particles;

[0025] 5) Immerse the adsorptive particles in a natural antibacterial solution for adsorption to obtain adsorptive antibacterial particles.

[0026] In the process of preparing the adsorptive antibacterial particles of the present invention, firstly, through amino modification, amino groups are grafted onto the mesoporous silica. Subsequently, due to its hollow cavity, when immersed in the carboxymethyl cellulose solution, the carboxymethyl cellulose solution can be filled into the hollow cavity. Under the subsequent cross-linking action of glyoxal, the carboxymethyl cellulose filled into the hollow cavity undergoes a cross-linking reaction to form a three-dimensional network structure, preventing the carboxymethyl cellulose from escaping. Then, calcination is carried out, and the carboxymethyl cellulose in the cavity forms an adsorptive porous material. Immersing it in the natural antibacterial solution can better adsorb the natural antibacterial solution, enhancing its antibacterial performance. At the same time, the silica shell can play a good protective role, preventing the antibacterial agent from being lost due to friction. Meanwhile, its adsorption effect can also adsorb odors during use, playing a role in deodorization. Finally, during the coating process of the antibacterial polymer, the amino groups grafted on the mesoporous silica can form chemical bonds with the antibacterial polymer, increasing the binding property.

[0027] Preferably, the cross-linking reaction is carried out at 50 - 70 °C for 5 - 10 h, and the calcination is carried out at 350 - 400 °C for 10 - 15 h.

[0028] Preferably, the polymerization in step three is carried out at 60 - 90 °C for 5 - 10 h.

[0029] Preferably, the addition amount of the adsorptive antibacterial particles in step three is 1 - 3 wt% of the prepolymerization liquid.

[0030] Therefore, the present invention has the following beneficial effects: First, a prepolymer with a block antibacterial structure is prepared. Subsequently, the adsorptive antibacterial particles are mixed with the prepolymerized liquid, and then polymerization is carried out, so that the periphery of the adsorptive antibacterial particles can be coated with a polymer having antibacterial effects. When in use, first, the outer antibacterial polymer layer has good antibacterial effects. At the same time, due to its coating effect, the antibacterial polymer layer can play a good slow-release role on the antibacterial agent in the adsorptive antibacterial particles. Under the action of the internal and external antibacterial effects, the antibacterial agent not only has strong antibacterial ability but also has long-lasting antibacterial performance. Moreover, the present invention needs to carry out prepolymerization first because when the adsorptive antibacterial particles are added, the prepolymer can first play a certain coating role to prevent the antibacterial agent in the adsorptive antibacterial particles from being released during the preparation process, so that the finally prepared antibacterial agent has good antibacterial effects. Detailed Embodiments

[0031] The following further describes the present invention in conjunction with the detailed embodiments.

[0032] Example 1:

[0033] A preparation method of a long-acting adsorptive deodorant and antibacterial agent, the preparation steps are as follows:

[0034] I. Put 5 parts of 1,4-benzenediacetic acid, 3 parts of dimethyl terephthalate, 7 parts of polyvinyl alcohol, and 8 parts of antibacterial monomer into deionized water and stir to obtain a 5 wt% mixed liquid;

[0035] The preparation steps of the antibacterial monomer are as follows:

[0036] Put 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol into an ethanol solvent and carry out a modification reaction at 60 °C, and then evaporate the solvent to prepare an antibacterial monomer; the mass ratio of the 5,5-dimethylhydantoin to the 2-chloropropane-1,3-diol is 3:1;

[0037] II. Carry out prepolymerization on the mixed liquid, the prepolymerization temperature is 50 °C, and the time is 2 h to obtain a prepolymerized liquid;

[0038] III. Add the adsorptive antibacterial particles to the prepolymerized liquid, the addition amount of the adsorptive antibacterial particles is 2 wt% of the prepolymerized liquid, and add the crosslinking agent glyoxal, stir and heat for polymerization until the liquid becomes thick to obtain a thick liquid; the polymerization is carried out at 70 °C for 4 h;

[0039] The preparation steps of the adsorptive antibacterial particles in step III are as follows:

[0040] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification;

[0041] 2) Immerse the amino-modified silica in the carboxymethyl cellulose solution and stir to disperse it, and fill the carboxymethyl cellulose solution into the hollow cavity of the amino-modified silica;

[0042] 3) Place the silica filled with the carboxymethyl cellulose solution into an aqueous glyoxal solution for cross-linking reaction, and the cross-linking reaction is carried out at 60 °C for 7 h;

[0043] 4) Calcinate the cross-linked silica at 370 °C for 12 h to obtain adsorption-type particles;

[0044] 5) Place the adsorption-type particles into the natural artemisia argyi antibacterial solution for adsorption to obtain adsorption-type antibacterial particles;

[0045] IV. Place the thick material in an oven for drying, and prepare a long-acting adsorption-type deodorant and antibacterial agent after grinding.

[0046] Example 2:

[0047] A preparation method of a long-acting adsorption-type deodorant and antibacterial agent, and the preparation steps are as follows:

[0048] I. Put 10 parts of 1,4-benzenediacetic acid, 1 part of methyl terephthalate, 2 parts of polyvinyl alcohol, and 10 parts of an antibacterial monomer into deionized water and stir to obtain a 3 wt% mixed material liquid;

[0049] The preparation steps of the antibacterial monomer are as follows:

[0050] Put 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol into an ethanol solvent, carry out a modification reaction at 60 °C, and then evaporate the solvent to prepare an antibacterial monomer; wherein the mass ratio of 5,5-dimethylhydantoin to 2-chloropropane-1,3-diol is 2:1;

[0051] II. Carry out prepolymerization on the mixed material liquid, the prepolymerization temperature is 40 °C, and the time is 3 h to obtain a prepolymerized material liquid;

[0052] III. Add the adsorption-type antibacterial particles to the prepolymerized material liquid, the addition amount of the adsorption-type antibacterial particles is 3 wt% of the prepolymerized material liquid, and add a cross-linking agent glyoxal, stir and heat to polymerize until the material liquid becomes thick to obtain a thick material; the polymerization is carried out at 60 °C for 5 h;

[0053] The preparation steps of the adsorption-type antibacterial particles in step III are as follows:

[0054] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification;

[0055] 2) Immerse the amino-modified silica in the carboxymethyl cellulose solution and stir to disperse it, filling the hollow cavity of the amino-modified silica with the carboxymethyl cellulose solution;

[0056] 3) Place the silica filled with the carboxymethyl cellulose solution in an aqueous glyoxal solution for crosslinking reaction, and the crosslinking reaction is carried out at 50 °C for 10 h;

[0057] 4) Calcinate the crosslinked silica at 350 °C for 15 h to obtain the adsorption-type particles;

[0058] 5) Place the adsorption-type particles in the natural Artemisia argyi antibacterial solution for adsorption to obtain the adsorption-type antibacterial particles;

[0059] IV. Place the thick material in an oven for drying, and after grinding, prepare a long-acting adsorption-type deodorant and antibacterial agent.

[0060] Example 3:

[0061] A preparation method of a long-acting adsorption-type deodorant and antibacterial agent, and the preparation steps are as follows:

[0062] I. Put 7 parts of 1,4-benzenediacetic acid, 5 parts of dimethyl terephthalate, 5 parts of polyvinyl alcohol, and 5 parts of antibacterial monomer into deionized water and stir to obtain a 10 wt% mixed material solution;

[0063] The preparation steps of the antibacterial monomer are as follows:

[0064] Put 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol into an ethanol solvent, carry out a modification reaction at 70 °C, and then evaporate the solvent to prepare the antibacterial monomer; wherein the mass ratio of 5,5-dimethylhydantoin to 2-chloropropane-1,3-diol is 4:1;

[0065] II. Carry out prepolymerization on the mixed material solution, the prepolymerization temperature is 40 °C, and the time is 3 h to obtain a prepolymerized material solution;

[0066] III. Add the adsorption-type antibacterial particles to the prepolymerized material solution, the addition amount of the adsorption-type antibacterial particles is 1 wt% of the prepolymerized material solution, and add the crosslinking agent glyoxal, stir and heat to polymerize until the material solution becomes thick to obtain a thick material; the polymerization is carried out at 90 °C for 3 h;

[0067] The preparation steps of the adsorption-type antibacterial particles in step III are as follows:

[0068] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification;

[0069] 2) Immerse the amino-modified silica in the carboxymethyl cellulose solution and stir to disperse, filling the carboxymethyl cellulose solution into the hollow cavity of the amino-modified silica;

[0070] 3) Place the silica filled with the carboxymethyl cellulose solution into an aqueous glyoxal solution for cross-linking reaction, and the cross-linking reaction is carried out at 70 °C for 5 h;

[0071] 4) Calcinate the silica after the cross-linking reaction at 400 °C for 10 h to obtain the adsorption-type particles;

[0072] 5) Place the adsorption-type particles into the natural artemisia argyi antibacterial solution for adsorption to obtain the adsorption-type antibacterial particles;

[0073] IV. Place the thick material in an oven for drying, and after grinding, prepare a long-acting adsorption-type deodorant and antibacterial agent.

[0074] Example 4:

[0075] A preparation method of a long-acting adsorption-type deodorant and antibacterial agent, and the preparation steps are as follows:

[0076] I. Put 5 - 10 parts of 1,4-benzenediacetic acid, 1 - 5 parts of dimethyl terephthalate, 2 - 7 parts of polyvinyl alcohol, and 5 - 10 parts of antibacterial monomer into deionized water and stir to obtain a 3 - 10 wt% mixed material liquid;

[0077] The preparation steps of the antibacterial monomer are as follows:

[0078] Put 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol into an ethanol solvent, carry out a modification reaction at 50 - 70 °C, and then evaporate the solvent to prepare the antibacterial monomer; wherein the mass ratio of 5,5-dimethylhydantoin to 2-chloropropane-1,3-diol is 2 - 4:1;

[0079] II. Carry out pre-polymerization on the mixed material liquid, the temperature of the pre-polymerization is 40 - 70 °C, and the time is 1 - 3 h to obtain a pre-polymerized material liquid;

[0080] III. Add the antibacterial particles to the pre-polymerized material liquid, the addition amount of the adsorption-type antibacterial particles is 1 - 3 wt% of the pre-polymerized material liquid, and add the cross-linking agent glyoxal, stir and heat for polymerization until the material liquid becomes thick to obtain a thick material; the polymerization is carried out at 60 - 90 °C for 3 - 5 h;

[0081] The preparation steps of the adsorption-type antibacterial particles in step III are as follows:

[0082] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification;

[0083] 2) Immerse the amino-modified silica in natural Artemisia argyi antibacterial liquid for adsorption to obtain antibacterial particles;

[0084] IV. Dry the thick material in an oven, grind it, and prepare a long-acting adsorption type odor and deodorant antibacterial agent.

[0085] Example 5:

[0086] A preparation method of a long-acting adsorption type odor and deodorant antibacterial agent, and the preparation steps are as follows:

[0087] I. Put 5 - 10 parts of 1,4-benzenediacetic acid, 1 - 5 parts of methyl terephthalate, 2 - 7 parts of polyvinyl alcohol, and 5 - 10 parts of antibacterial monomer into deionized water and stir to obtain a 3 - 10 wt% mixture liquid;

[0088] The preparation steps of the antibacterial monomer are as follows:

[0089] Put 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol into an ethanol solvent, carry out a modification reaction at 50 - 70 °C, and then evaporate the solvent to prepare an antibacterial monomer; wherein the mass ratio of 5,5-dimethylhydantoin to 2-chloropropane-1,3-diol is 2 - 4:1;

[0090] II. Carry out pre-polymerization on the mixture liquid, the temperature of the pre-polymerization is 40 - 70 °C, and the time is 1 - 3 h to obtain a pre-polymerized liquid;

[0091] III. Add the adsorption type antibacterial particles to the pre-polymerized liquid, the addition amount of the adsorption type antibacterial particles is 1 - 3 wt% of the pre-polymerized liquid, and add cross-linking agent glyoxal, stir and heat to polymerize until the liquid becomes thick to obtain a thick material; the polymerization is carried out at 60 - 90 °C for 3 - 5 h;

[0092] The preparation steps of the adsorption type antibacterial particles in step III are as follows:

[0093] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification;

[0094] 2) Immerse the amino-modified silica in a carboxymethyl cellulose solution and stir to disperse, and fill the carboxymethyl cellulose solution in the hollow cavity of the amino-modified silica;

[0095] 3) Calcinate the silica at 350 - 400 °C for 10 - 15 h to obtain adsorption type particles;

[0096] 4) Immerse the adsorption type particles in natural Artemisia argyi antibacterial liquid for adsorption to obtain adsorption type antibacterial particles;

[0097] IV. Place the thick material in an oven for drying, and after grinding, a long-acting adsorption type deodorizing and antibacterial agent is prepared.

[0098] Comparative Example 1:

[0099] A preparation method of a long-acting adsorption type deodorizing and antibacterial agent, and the preparation steps are as follows:

[0100] I. Place 5 parts of 1,4-benzenediacetic acid, 3 parts of dimethyl terephthalate, and 7 parts of polyvinyl alcohol in deionized water and stir to obtain a 5 wt% mixed material liquid;

[0101] II. Carry out prepolymerization on the mixed material liquid, the prepolymerization temperature is 50 °C, and the time is 2 h to obtain a prepolymerized material liquid;

[0102] III. Add the adsorption type antibacterial particles to the prepolymerized material liquid, the addition amount of the adsorption type antibacterial particles is 2 wt% of the prepolymerized material liquid, and add the crosslinking agent glyoxal, stir and heat for polymerization until the material liquid becomes thick to obtain a thick material; the polymerization is carried out at 70 °C for 4 h;

[0103] The preparation steps of the adsorption type antibacterial particles in step III are as follows:

[0104] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification;

[0105] 2) Immerse the amino-modified silica in a carboxymethyl cellulose solution and stir to disperse, and fill the carboxymethyl cellulose solution in the hollow cavity of the amino-modified silica;

[0106] 3) Place the silica filled with the carboxymethyl cellulose solution in an aqueous glyoxal solution for crosslinking reaction, and the crosslinking reaction is carried out at 60 °C for 7 h;

[0107] 4) Calcinate the crosslinked silica at 370 °C for 12 h to obtain adsorption type particles;

[0108] 5) Place the adsorption type particles in a natural artemisia argyi antibacterial solution for adsorption to obtain adsorption type antibacterial particles;

[0109] IV. Place the thick material in an oven for drying, and after grinding, a long-acting adsorption type deodorizing and antibacterial agent is prepared.

[0110] Comparative Example 2:

[0111] A preparation method of a long-acting adsorption type deodorizing and antibacterial agent, and the preparation steps are as follows:

[0112] I. Place 5 parts of 1,4-benzenediacetic acid, 3 parts of dimethyl terephthalate, 7 parts of polyvinyl alcohol, and 8 parts of 5,5-dimethylhydantoin in deionized water and stir to obtain a 5 wt% mixed material liquid;

[0113] II. Pre-polymerize the mixture liquid at a temperature of 50 °C for 2 h to obtain a pre-polymerized liquid.

[0114] III. Add the adsorptive antibacterial particles to the pre-polymerized liquid. The addition amount of the adsorptive antibacterial particles is 2 wt% of the pre-polymerized liquid, and add glyoxal as a cross-linking agent. Stir and heat to polymerize until the liquid becomes thick to obtain a thick liquid. The polymerization is carried out at 70 °C for 4 h.

[0115] The preparation steps of the adsorptive antibacterial particles in step III are as follows:

[0116] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% aminopropyltriethoxysilane solution for amino modification.

[0117] 2) Immerse the amino-modified silica in a carboxymethyl cellulose solution and stir to disperse it, and fill the carboxymethyl cellulose solution in the hollow cavity of the amino-modified silica.

[0118] 3) Place the silica filled with the carboxymethyl cellulose solution in an aqueous glyoxal solution for cross-linking reaction. The cross-linking reaction is carried out at 60 °C for 7 h.

[0119] 4) Calcinate the cross-linked silica at 370 °C for 12 h to obtain adsorptive particles.

[0120] 5) Place the adsorptive particles in a natural artemisia argyi antibacterial solution for adsorption to obtain adsorptive antibacterial particles.

[0121] IV. Place the thick liquid in an oven for drying, grind it, and prepare a long-acting adsorptive deodorizing and antibacterial agent.

[0122] Comparative Example 3:

[0123] A preparation method of a long-acting adsorptive deodorizing and antibacterial agent. The preparation steps are as follows:

[0124] I. Place 5 parts of 1,4-benzenediacetic acid, 3 parts of dimethyl terephthalate, 7 parts of polyvinyl alcohol, and 8 parts of an antibacterial monomer in deionized water and stir to obtain a 5 wt% mixture liquid.

[0125] The preparation steps of the antibacterial monomer are as follows:

[0126] Place 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol in an ethanol solvent and carry out a modification reaction at 60 °C. Then evaporate the solvent to prepare the antibacterial monomer. The mass ratio of 5,5-dimethylhydantoin to 2-chloropropane-1,3-diol is 3:1.

[0127] III. Add the adsorptive antibacterial particles into the prepolymerized liquid. The addition amount of the adsorptive antibacterial particles is 2 wt% of the mixed liquid, and add the crosslinking agent glyoxal. Stir and heat for polymerization until the liquid becomes thick to obtain a thick liquid; the polymerization is carried out at 70 °C for 6 h;

[0128] The preparation steps of the adsorptive antibacterial particles in Step III are as follows:

[0129] 1) Immerse the mesoporous silica with a hollow cavity in a 3 wt% 3-aminopropyltriethoxysilane solution for amino modification;

[0130] 2) Immerse the amino-modified silica in a carboxymethyl cellulose solution and stir to disperse it, and fill the carboxymethyl cellulose solution in the hollow cavity of the amino-modified silica;

[0131] 3) Place the silica filled with the carboxymethyl cellulose solution in an aqueous glyoxal solution for crosslinking reaction. The crosslinking reaction is carried out at 60 °C for 7 h;

[0132] 4) Calcinate the crosslinked silica at 370 °C for 12 h to obtain adsorptive particles;

[0133] 5) Place the adsorptive particles in a natural artemisia antibacterial liquid for adsorption to obtain adsorptive antibacterial particles;

[0134] IV. Place the thick liquid in an oven for drying, and prepare a long-acting adsorptive deodorant and antibacterial agent after grinding.

[0135] Mix the antibacterial particles prepared in the examples and comparative examples with an acrylate emulsion to prepare an antibacterial coating, and spray it onto a test metal plate to prepare a coating with a thickness of 50 μm.

[0136] Test according to the national standard GB / T 21866-2008 Determination Method and Antibacterial Effect of Antibacterial Coatings (Paint Films). The sterilization rate at 5 h after the culture surface was contaminated by bacteria was measured for the untreated coating and the worn coating (the coating was washed, wiped, and air-dried in a cycle for 48 h for long-term testing). The experimental strain was selected as Escherichia coli.

[0137]

[0138] As can be seen from the above-mentioned examples and comparative examples, the antibacterial agent prepared by the present invention has good antibacterial effects, and still has good effects after the loss treatment; in Example 4 and Example 5, there is no carboxymethyl cellulose or the carboxymethyl cellulose is not cross-linked in the antibacterial particles, so the adsorption is insufficient, resulting in a decrease in the antibacterial effect after the loss treatment. In Comparative Example 1 and Comparative Example 2, there is no antibacterial 5,5-dimethylhydantoin or the antibacterial 5,5-dimethylhydantoin is not modified, so block copolymerization cannot be carried out, resulting in poor antibacterial effects; in Comparative Example 3, due to no prepolymerization, the adsorbed natural antibacterial agent is less, and the effect is poor after the loss treatment.

Claims

1. A preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The preparation steps are as follows: I. Put 1,4-benzenediacetic acid, methyl terephthalate, polyvinyl alcohol and an antibacterial monomer into deionized water and stir to obtain a mixed material liquid; II. Carry out prepolymerization on the mixed material liquid to obtain a prepolymerized material liquid; III. Add the adsorption type antibacterial particles into the prepolymerized material liquid, add a crosslinking agent, stir and heat to polymerize until the material liquid becomes thick to obtain a thick material; IV. Dry the thick material in an oven, grind it, and prepare a long-acting adsorption type odor and deodorization antibacterial agent; The preparation steps of the antibacterial monomer in step I are as follows: Put 5,5-dimethylhydantoin and 2-chloropropane-1,3-diol into an ethanol solvent, carry out a modification reaction at 50-70 °C, and then evaporate the solvent to prepare an antibacterial monomer; The preparation steps of the adsorption type antibacterial particles in step III are as follows: 1) Immerse mesoporous silica with a hollow cavity in an aminopropyltriethoxysilane solution for amino modification; 2) Immerse the amino-modified silica in a carboxymethyl cellulose solution and stir to disperse it, and fill the carboxymethyl cellulose solution in the hollow cavity of the amino-modified silica; 3) Put the silica filled with the carboxymethyl cellulose solution into an aqueous glyoxal solution for crosslinking reaction; 4) Calcinate the crosslinked silica to obtain adsorption type particles; 5) Adsorb the adsorption type particles in a natural antibacterial liquid to obtain adsorption type antibacterial particles.

2. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The mass parts of each component in step I are: 5-10 parts of 1,4-benzenediacetic acid, 1-5 parts of methyl terephthalate, 2-7 parts of polyvinyl alcohol, and 5-10 parts of an antibacterial monomer.

3. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The concentration of the mixed material liquid in step I is 3-10 wt%.

4. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The mass ratio of the 5,5-dimethylhydantoin to the 2-chloropropane-1,3-diol is 2-4:

1.

5. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The temperature of the prepolymerization in step II is 40-70 °C, and the time is 1-3 h.

6. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The crosslinking reaction is carried out at 50-70 °C for 5-10 h, and the calcination is carried out at 350-400 °C for 10-15 h.

7. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The polymerization in step III is carried out at 60-90 °C for 3-5 h.

8. According to claim 1, a preparation method of a long-acting adsorption type odor and deodorization antibacterial agent, characterized in that The addition amount of the adsorption type antibacterial particles in step III is 1-3 wt% of the prepolymerized material liquid.

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