阅读说明：本技术 一种抗菌耐盐高吸水树脂及其制备方法和应用 (Antibacterial salt-resistant super absorbent resin and preparation method and application thereof ) 是由 刘妙锋 程程 陈东飞 韩露 于 2019-11-05 设计创作，主要内容包括：本发明公开了一种抗菌耐盐高吸水树脂及其制备方法和应用。抗菌耐盐高吸水树脂的制备方法包括以下步骤：S1、将丙烯酸、去离子水和碱液混合；S2、向丙烯酸碱液中加入初交联剂,搅拌均匀,加入Ag-SiO<Sub>2</Sub>复合抗菌剂插层石墨烯抗菌组合物；S3、加入引发剂,反应0.5-3min,加入复合纤维,得到凝胶状聚合物；S4、将胶凝状聚合物进行造粒、干燥；S5、将芳香族聚酰胺和纳米银离子熔融挤出,向熔融组分中加入离子交换树脂和复合交联剂,加压喷雾法对所有颗粒状聚合物进行热表面处理。本发明的抗菌耐盐高吸水树脂可用于一次性纸尿裤,其具有能分离和消除尿液中的各种无机盐成分,快速排出湿气和热气,干爽舒适,且抑制细菌,预防婴儿红臀的优点。(The invention discloses an antibacterial salt-resistant super absorbent resin, and a preparation method and application thereof. The preparation method of the antibacterial salt-resistant super absorbent resin comprises the following steps: s1, mixing acrylic acid, deionized water and alkali liquor; s2, adding a primary cross-linking agent into the acrylic acid alkali liquor, stirring uniformly, adding Ag-SiO 2 A composite antimicrobial intercalated graphene antimicrobial composition; s3, adding an initiator, reacting for 0.5-3min, and adding composite fibers to obtain a gel polymer; s4, granulating and drying the gelatinous polymer; s5, melting and extruding the aromatic polyamide and the nano silver ions, adding the ion exchange resin and the composite cross-linking agent into the molten components, and carrying out thermal surface treatment on all granular polymers by a pressurized spraying method. The antibacterial salt-resistant super absorbent resin can be used for disposable paper diapers, and has the advantages of separating and eliminating various inorganic salt components in urine, quickly discharging moisture and hot air, being dry and comfortable, inhibiting bacteria and preventing red buttocks of infants.)

1. A preparation method of antibacterial salt-resistant super absorbent resin is characterized by comprising the following steps:

s1, mixing acrylic acid, deionized water and alkali liquor to obtain partially neutralized acrylic acid alkali liquor;

s2, adding a primary cross-linking agent into the acrylic acid alkali liquor, stirring uniformly, and adding Ag-SiO₂Carrying out ultrasonic dispersion on the composite antibacterial agent intercalated graphene antibacterial composition for 30-60 min;

s3, heating to 35-70 ℃, adding an initiator for polymerization reaction for 0.5-3min, adding composite fibers, and uniformly stirring to obtain a gel polymer;

s4, granulating and drying the gelatinous polymer to obtain a granular polymer;

s5, placing aromatic polyamide and nano silver ions at 280 ℃ for melt extrusion to prepare a molten component, adding ion exchange resin and a composite cross-linking agent into the molten component, uniformly mixing, performing thermal surface treatment on all granular polymers at 250 ℃ under 200 ℃ and by adopting a pressurized spraying method, stirring and mixing, and drying to prepare the antibacterial salt-resistant super absorbent resin; the dosage of the ion exchange resin is 60-80% of the mass of the molten component, and the mass ratio of the dosage of the molten component to the granular polymer is 1: 0.6-0.8.

2. The method for preparing antibacterial salt-resistant super absorbent resin according to claim 1, wherein the Ag-SiO₂The composite antibacterial agent intercalated graphene antibacterial composition is prepared by the following method:

(1) mixing 0.4-0.8 part by weight of nano silicon powder and 0.8-1.2 parts by weight of silver ammonia solution, adjusting the pH value of the mixed solution to 9.0-9.5, adding 0.3-0.7 part by weight of chitosan and 0.2-0.6 part by weight of absolute ethyl alcohol, and uniformly mixing to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution, filtering to obtain a solid product, drying and crushing the solid product to obtain Ag-SiO₂A composite antimicrobial agent;

(3) mixing Ag-SiO₂Dissolving the composite antibacterial agent in deionized water to form 5-20% Ag-SiO2 composite antibacterial solution, oxidizingAdding graphene into deionized water to prepare a graphene oxide solution with the concentration of 0.2-20ml/L, and ultrasonically dispersing the graphene oxide solution for 30-40min to form a graphene oxide suspension;

(4) mixing Ag-SiO₂Adding the composite antibacterial solution into the graphene oxide suspension, performing ultrasonic dispersion for 40-100min, freezing, and drying to obtain Ag-SiO₂The composite antibacterial agent is intercalated with the graphene antibacterial composition.

3. The method for preparing the antibacterial salt-resistant super absorbent resin according to claim 1, wherein the composite fiber is prepared by the following method: (1) adding 0.3-0.7 weight part of carboxymethyl chitosan into 0.9-1.2 weight parts of water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution;

(2) placing 0.6-0.8 weight parts of tea saponin, 0.3-0.5 weight parts of montmorillonite and 0.7-0.9 weight parts of sepiolite into a nanometer grinding machine, and grinding for 30-50min to obtain nanometer fine powder;

(3) adding the nanometer fine powder into the carboxymethyl chitosan solution, stirring uniformly, and preparing the composite fiber through wet spinning, wherein the mass ratio of the nanometer fine powder to the carboxymethyl chitosan solution is (0.7-0.9): 1.

4. The preparation method of the antibacterial salt-tolerant super absorbent resin as claimed in claim 1, wherein the antibacterial salt-tolerant super absorbent resin comprises the following raw materials in parts by weight: 40-50 parts of acrylic acid, 20-30 parts of deionized water, 15-20 parts of alkali liquor, 0.05-0.9 part of primary cross-linking agent and 1-10 parts of Ag-SiO₂The composite antibacterial agent intercalated graphene antibacterial composition comprises 0.03-1.5 parts of initiator, 3-7 parts of composite fiber, 60-80 parts of aromatic polyamide, 30-40 parts of nano silver ions, 20-30 parts of ion exchange resin and 0.03-0.05 part of composite cross-linking agent.

5. The method for preparing the antibacterial salt-tolerant super absorbent resin according to claim 1, wherein the alkali liquor is one or a combination of more of aqueous solutions prepared from sodium hydroxide, potassium hydroxide or ammonium carbonate;

the primary cross-linking agent is one of N, N-methylene bisacrylamide, polyethylene glycol 200, butanediol, pentaerythritol and trihydroxymethane triacrylate;

the initiator is one or a combination of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide.

6. The method for preparing the antibacterial salt-tolerant super absorbent resin according to claim 1, wherein the composite cross-linking agent is one or more of ethers, esters and alcohol cross-linking agents containing two or more hydroxyl groups, the ether cross-linking agent is polyethylene glycol diglycidyl oil ether, the ester cross-linking agent is one or two of polyethylene glycol 200 diacrylate and trimethylolmethane triacrylate, and the alcohol cross-linking agent is one or more of polyethylene glycol 200, butanediol and pentaerythritol.

7. The preparation method of the antibacterial salt-tolerant super absorbent resin as claimed in claim 1, wherein the ion exchange resin is one of strongly acidic styrene cation exchange resin, strongly basic styrene anion exchange resin, macroporous weakly acidic styrene cation exchange resin, strongly homogeneous pore bispolystyrene cation resin, macroporous strongly basic quaternary ammonium cation exchange resin, macroporous weakly acidic acrylic cation exchange resin, macroporous weakly basic acrylic anion exchange resin, macroporous weakly acidic acrylic anion exchange resin or macroporous styrene chelating ion exchange resin.

8. An antibacterial salt-tolerant super absorbent resin, which is prepared by the preparation method of the antibacterial salt-tolerant super absorbent resin according to any one of claims 1 to 7.

9. The use of the antibacterial salt-tolerant super absorbent resin prepared by the preparation method of the antibacterial salt-tolerant super absorbent resin according to any one of claims 1 to 7 in disposable diapers.

10. The use of the antibacterial salt-tolerant super absorbent resin as claimed in claim 9, wherein the disposable diaper comprises dust-free paper, antibacterial salt-tolerant super absorbent resin, non-woven fabric, antibacterial salt-tolerant super absorbent resin and dust-free paper in sequence.

Technical Field

The invention relates to the technical field of high polymer resin, in particular to an antibacterial salt-resistant super absorbent resin and a preparation method and application thereof.

Background

The infant paper diaper is a nursing product designed for infants, so that the product is convenient to use and replace, and the burden of nursing staff is relieved. With the change of consumption concepts of young parents and the acceleration of life rhythm, the infant paper diaper gradually replaces the traditional diaper and becomes a necessity for family infant care.

Diapers generally consist of three main parts: the paper diaper mainly comprises a surface coating layer, an absorption core layer and a base fabric, wherein the absorption core layer is mainly a layered structure which can capture and quickly absorb urine, disperse the urine or diffuse the urine into the whole core layer through capillary action and finally absorb and store the urine, and the layered structure mainly comprises pure wood pulp (fluff pulp) and Super Absorbent Polymer (SAP), and the super absorbent polymer plays a very critical role in the paper diaper, so the urine of a baby can be completely absorbed by the paper diaper due to very large water absorption capacity.

Because the urine of children mainly contains urea and various inorganic salt ions, such as sodium ions, chloride ions, potassium ions, sulfate ions and the like, and meanwhile, the urine of people is converted into ammonia smell with unpleasant taste under the action of various microorganisms, but the super absorbent resin belongs to high polymer electrolyte, and various ion components can generate a homoionic effect on the water absorption process of the super absorbent resin, so that the components have great influence on the water absorption capacity of the super absorbent resin, which shows that the absorption rate of the super absorbent resin is greatly reduced, so that the absorption performance of the paper diaper on the urine is reduced, the urine absorption capacity of the paper diaper is reduced, the urine leakage is easy to occur, hot air and moisture are difficult to discharge quickly, the dryness is reduced, and simultaneously, because the skin of the tender of infants is easy to infect bacteria when being used for a long time, the skin rash and the like are caused.

Disclosure of Invention

Aiming at the defects in the prior art, the first object of the invention is to provide a preparation method of an antibacterial salt-tolerant super absorbent resin, which has the advantages that the prepared antibacterial salt-tolerant super absorbent resin can separate and eliminate various inorganic salt components in urine, quickly discharge moisture and hot air, is dry and comfortable, inhibits bacteria and prevents red buttocks of infants.

The second purpose of the invention is to provide an antibacterial salt-tolerant super absorbent resin which has the advantages of separating and eliminating various inorganic salt components in urine, rapidly discharging moisture and hot air, being dry and comfortable, inhibiting bacteria and preventing red buttocks.

The third purpose of the invention is to provide the application of the antibacterial salt-resistant super absorbent resin, which has the advantages of separating and eliminating various inorganic salt components in urine after being made into a paper diaper, rapidly discharging moisture and hot air, being dry and comfortable, inhibiting bacteria and preventing red buttocks.

In order to achieve the first object, the invention provides the following technical scheme: a preparation method of antibacterial salt-resistant super absorbent resin comprises the following steps:

s1, mixing acrylic acid, deionized water and alkali liquor to obtain partially neutralized acrylic acid alkali liquor;

s2, adding a primary cross-linking agent into the acrylic acid alkali liquor, stirring uniformly, and adding Ag-SiO₂Carrying out ultrasonic dispersion on the composite antibacterial agent intercalated graphene antibacterial composition for 30-60 min;

s3, heating to 35-70 ℃, adding an initiator for polymerization reaction for 0.5-3min, adding composite fibers, and uniformly stirring to obtain a gel polymer;

s4, granulating and drying the gelatinous polymer to obtain a granular polymer;

s5, placing aromatic polyamide and nano silver ions at 280 ℃ for melt extrusion to prepare a molten component, adding ion exchange resin and a composite cross-linking agent into the molten component, uniformly mixing, performing thermal surface treatment on all granular polymers at 250 ℃ under 200 ℃ and by adopting a pressurized spraying method, stirring and mixing, and drying to prepare the antibacterial salt-resistant super absorbent resin; the dosage of the ion exchange resin is 60-80% of the mass of the molten component, and the mass ratio of the dosage of the molten component to the granular polymer is 1: 0.6-0.8.

By adopting the technical scheme, the Ag-SiO is adopted₂Composite antimicrobial intercalated graphene antimicrobial compositions via graphene oxide and Ag-SiO₂The super absorbent resin has excellent antibacterial performance on staphylococcus aureus, escherichia coli, candida and the like due to the synergistic effect of the composite antibacterial agent; because the graphene oxide contains rich oxygen-containing functional groups, the crosslinking effect is strong, chemical acting force can be generated between the graphene oxide and a polymer molecular chain and between the graphene oxide and the polymer molecular chain, the strength and the crosslinking degree of the polymer molecular chain serving as a molecular framework are improved, and because the layered graphene oxide serves as a crosslinking point in a crosslinking network structure of the super absorbent resin, a more compact three-dimensional crosslinking network structure is formed, more space is provided for accommodating water molecules, the absorption capacity of the super absorbent resin is enhanced, meanwhile, the phenomenon that the polyelectrolyte network is structurally collapsed in a saline solution can be effectively relieved by the graphene oxide, and the salt resistance and the water absorption speed of the super absorbent resin are improved; the aromatic polyamide and the nano silver ions are melted and extruded and then are mixed with the ion exchange resinThe aromatic polyamide can filter organic salt components in the urine of the baby, reduce the concentration of the urine, namely reduce the homoionic effect of various ionic components in the urine on the super absorbent resin, and reduce the influence on the water absorption capacity of the super absorbent resin, so that the super absorbent resin has stronger liquid absorption rate and absorption capacity.

Further, the Ag-SiO₂The composite antibacterial agent intercalated graphene antibacterial composition is prepared by the following method:

(1) mixing 0.4-0.8 part by weight of nano silicon powder and 0.8-1.2 parts by weight of silver ammonia solution, adjusting the pH value of the mixed solution to 9.0-9.5, adding 0.3-0.7 part by weight of chitosan and 0.2-0.6 part by weight of absolute ethyl alcohol, and uniformly mixing to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution, filtering to obtain a solid product, drying and crushing the solid product to obtain Ag-SiO₂A composite antimicrobial agent;

(3) mixing Ag-SiO₂Dissolving a composite antibacterial agent in deionized water to form an Ag-SiO2 composite antibacterial solution with the concentration of 5-20%, adding graphene oxide into the deionized water to prepare a graphene oxide solution with the concentration of 0.2-20ml/L, and ultrasonically dispersing the graphene oxide solution for 30-40min to form a graphene oxide suspension;

(4) mixing Ag-SiO₂Adding the composite antibacterial solution into the graphene oxide suspension, performing ultrasonic dispersion for 40-100min, freezing, and drying to obtain Ag-SiO₂The composite antibacterial agent is intercalated with the graphene antibacterial composition.

By adopting the technical scheme, because the graphene oxide has porous property and contains rich oxygen-containing functional groups, the graphene oxide can destroy cell membranes, and meanwhile, the graphene can effectively relieve the structural collapse phenomenon of a polyelectrolyte network in a salt solution, improve the salt resistance and absorption rate of the antibacterial salt-tolerant super absorbent resin, and improve the Ag-SiO₂The composite antibacterial agent can destroy the protein structure of microorganisms to make bacteria lose activity or die, and after silver ions are loaded on silicon dioxide, the composite antibacterial agent can effectively reduce agglomeration, increase the contact surface with the bacteria, inhibit the growth of the bacteria, effectively improve the sterilization rate, and make Ag-SiO₂The composite antibacterial agent and the graphene oxide are compounded to prepare the antibacterial composition, so that the Ag-SiO₂The composite antibacterial agent and the graphene oxide form effective chemical bond linkage of hydrogen bonds, ionic bonds or/and covalent bonds through polar functional groups, so that the composite antibacterial agent and the graphene oxide have a synergistic effect, the antibacterial performance advantages are complementary, and the performance and the application range of the antibacterial composition are improved.

Further, the composite fiber is made by the following method: (1) adding 0.3-0.7 weight part of carboxymethyl chitosan into 0.9-1.2 weight parts of water, and stirring until the carboxymethyl chitosan is completely dissolved to obtain a carboxymethyl chitosan solution;

(2) placing 0.6-0.8 weight parts of tea saponin, 0.3-0.5 weight parts of montmorillonite and 0.7-0.9 weight parts of sepiolite into a nanometer grinding machine, and grinding for 30-50min to obtain nanometer fine powder;

(3) adding the nanometer fine powder into the carboxymethyl chitosan solution, stirring uniformly, and preparing the composite fiber through wet spinning, wherein the mass ratio of the nanometer fine powder to the carboxymethyl chitosan solution is (0.7-0.9): 1.

By adopting the technical scheme, the carboxymethyl chitosan has stronger antibacterial property, the tea saponin has excellent emulsification, dispersion, wetting, anti-permeation, anti-inflammation, sterilization and other effects, the antibacterial property of the super absorbent resin is enhanced, the dispersion property of montmorillonite and sepiolite in the carboxymethyl chitosan solution can also be improved, the hydrophilicity, the unique spatial structure and the surface active group of the montmorillonite and the sepiolite can improve the network structure of the super absorbent resin, the gel strength and the salt resistance of the antibacterial salt-tolerant super absorbent resin are improved, and the water absorption rate and the pressure absorption rate of the super absorbent resin are enhanced.

Further, the antibacterial salt-resistant super absorbent resin comprises the following raw materials in parts by weight: 40-50 parts of acrylic acid, 20-30 parts of deionized water, 15-20 parts of alkali liquor, 0.05-0.9 part of primary cross-linking agent and 1-10 parts of Ag-SiO₂The composite antibacterial agent intercalated graphene antibacterial composition comprises 0.03-1.5 parts of initiator, 3-7 parts of composite fiber, 60-80 parts of aromatic polyamide, 30-40 parts of nano silver ions, 20-30 parts of ion exchange resin and 0.03-0.05 part of composite cross-linking agent.

By adopting the technical scheme, the raw material proportion of the antibacterial salt-resistant super absorbent resin is reasonable, and the prepared super absorbent resin has the advantages of good antibacterial performance, high water absorption speed, large absorption capacity, small rewet capacity and better absorption performance.

Further, the alkali liquor is one or a combination of more of aqueous solutions prepared from sodium hydroxide, potassium hydroxide or ammonium carbonate;

the primary cross-linking agent is one of N, N-methylene bisacrylamide, polyethylene glycol 200, butanediol, pentaerythritol and trihydroxymethane triacrylate;

the initiator is one or a combination of potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide.

Further, the composite cross-linking agent is one or a combination of ethers, esters and alcohol cross-linking agents containing two or more hydroxyl groups, the ether cross-linking agent is polyethylene glycol diglycidyl oil ether, the ester cross-linking agent is one or two of polyethylene glycol 200 diacrylate and trimethylolmethane triacrylate, and the alcohol cross-linking agent is one or a combination of polyethylene glycol 200, butanediol and pentaerythritol.

Further, the ion exchange resin is one of strongly acidic styrene cation exchange resin, strongly basic styrene anion exchange resin, macroporous weakly acidic styrene cation exchange resin, strongly homogeneous porous bispolystyrene cation resin, macroporous strongly basic quaternary ammonium cation exchange resin, macroporous weakly acidic acrylic cation exchange resin, macroporous weakly basic acrylic anion exchange resin, macroporous weakly acidic acrylic anion exchange resin or macroporous styrene chelating ion exchange resin.

In order to achieve the second object, the invention provides the following technical scheme: an antibacterial salt-tolerant super absorbent resin is prepared by a preparation method of the antibacterial salt-tolerant super absorbent resin.

In order to achieve the third object, the invention provides the following technical solutions: an application of antibacterial salt-tolerant super absorbent resin prepared by a preparation method in disposable diapers.

Further, the disposable diaper sequentially comprises dust-free paper, antibacterial salt-resistant super absorbent resin, non-woven fabric, antibacterial salt-resistant super absorbent resin and dust-free paper.

By adopting the technical scheme, the paper diaper made of the antibacterial salt-resistant super absorbent resin has excellent absorption capacity and less rewet capacity, can keep the dryness and comfort of the buttocks of a baby and prevent the red buttocks.

In conclusion, the invention has the following beneficial effects:

firstly, the invention adopts Ag-SiO₂The graphene oxide antibacterial composition with the composite antibacterial agent intercalated can be matched with Ag-SiO due to more oxygen-containing functional groups₂The composite antibacterial agent is combined and has a synergistic effect, so that the hydrophilicity and osmotic pressure of the super absorbent resin are improved, the super absorbent resin has safe, quick-acting, slow-release and long-acting antibacterial performance, and simultaneously has high water retention and high salt tolerance absorbability, the gel strength of the super absorbent resin is prevented from being reduced after the super absorbent resin absorbs urine, or the gel is prevented from collapsing to cause the reduction of the liquid passing speed and the urine leakage, and the safety problems of red rash, skin itch, peculiar smell and the like of a baby when the super absorbent resin is used for disposable diapers are avoided.

Secondly, the aromatic polyamide and the ion exchange resin are adopted in the invention, the aromatic polyamide can filter organic salt components in urine, the pore structure and the three-dimensional network structure of the ion exchange resin can help the urine filtered with the organic salt components to quickly permeate to the surface of the high water-absorbent resin, and the ion exchange capacity of the ion exchange resin can exchange ions in the urine during filtering, so that various inorganic salt components in the urine of a baby are further separated and eliminated, and the water absorption capacity, the salt resistance and the liquid passing speed of the high water-absorbent resin in the paper diaper are greatly improved.

Thirdly, because the composite fiber is adopted in the invention and is prepared from carboxymethyl chitosan, poor saponin, montmorillonite, sepiolite and the like, the effects of antibiosis, antiphlogosis and the like of the super absorbent resin can be enhanced, the network structure of the super absorbent resin is improved, the gel strength and the salt tolerance of the super absorbent resin are improved, and the liquid passing speed of the super absorbent resin is increased.

Detailed Description

The present invention will be described in further detail with reference to examples.

Ag-SiO₂Preparation examples 1 to 3 of composite antibacterial agent intercalated graphene antibacterial composition

The nano silicon powder in preparation examples 1 to 3 is selected from nano silicon powder sold by Nanjing Baokte New Material Co., Ltd under the product number IC 010.

Preparation example 1: (1) mixing 0.4kg of nano silicon powder and 0.8kg of silver ammonia solution, adjusting the pH value of the mixed solution to 9.0, adding 0.3kg of chitosan and 0.2kg of absolute ethyl alcohol, and uniformly mixing to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution, filtering to obtain a solid product, drying and crushing the solid product to obtain Ag-SiO₂A composite antimicrobial agent;

(3) mixing Ag-SiO₂The composite antibacterial agent is dissolved in deionized water to form 5% Ag-SiO₂Compounding an antibacterial solution, namely adding graphene oxide into deionized water to prepare a graphene oxide solution with the concentration of 0.2ml/L, and ultrasonically dispersing the graphene oxide solution for 30min to form a graphene oxide suspension;

(4) mixing Ag-SiO₂Adding the composite antibacterial solution into the graphene oxide suspension, performing ultrasonic dispersion for 40min, and performing freezing and drying to obtain Ag-SiO₂The composite antibacterial agent is intercalated with the graphene antibacterial composition.

Preparation example 2: (1) mixing 0.6kg of nano silicon powder and 1.0kg of silver ammonia solution, adjusting the pH value of the mixed solution to 9.3, adding 0.5kg of chitosan and 0.4kg of absolute ethyl alcohol, and uniformly mixing to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution, filtering to obtain a solid product, drying and crushing the solid product to obtain Ag-SiO₂A composite antimicrobial agent;

(3) mixing Ag-SiO₂Dissolving the composite antibacterial agent in deionized water to form Ag-SiO with the concentration of 15%₂Compounding an antibacterial solution, adding graphene oxide into deionized water to prepare a graphene oxide solution with the concentration of 10ml/L, and ultrasonically dispersing the graphene oxide solution for 35min to form a graphene oxide suspension；

(4) Mixing Ag-SiO₂Adding the composite antibacterial solution into the graphene oxide suspension, performing ultrasonic dispersion for 70min, and performing freezing and drying to obtain Ag-SiO₂The composite antibacterial agent is intercalated with the graphene antibacterial composition.

Preparation example 3: (1) mixing 0.8kg of nano silicon powder and 1.2kg of silver ammonia solution, adjusting the pH value of the mixed solution to 9.5, adding 0.7kg of chitosan and 0.6kg of absolute ethyl alcohol, and uniformly mixing to obtain a mixed solution;

(2) carrying out ultrasonic treatment on the mixed solution, filtering to obtain a solid product, drying and crushing the solid product to obtain Ag-SiO₂A composite antimicrobial agent;

(3) mixing Ag-SiO₂Dissolving the composite antibacterial agent in deionized water to form 20% Ag-SiO₂Compounding an antibacterial solution, namely adding graphene oxide into deionized water to prepare a graphene oxide solution with the concentration of 20ml/L, and ultrasonically dispersing the graphene oxide solution for 40min to form a graphene oxide suspension;

(4) mixing Ag-SiO₂Adding the composite antibacterial solution into the graphene oxide suspension, performing ultrasonic dispersion for 100min, and performing freezing and drying to obtain Ag-SiO₂The composite antibacterial agent is intercalated with the graphene antibacterial composition.

Preparation examples 4 to 6 of conjugate fibers

In preparation examples 4 to 6, the carboxymethyl chitosan was selected from carboxymethyl chitosan sold under the trade name of 002 by santa sergeani biotechnology limited, the tea saponin was selected from tea saponin sold under the trade name of TK-3772 by santac biotechnology limited, shanxi, the montmorillonite was selected from montmorillonite sold under the trade name of 099 by the manufacturer of cis-rock ore products in the guy county, and the sepiolite was selected from sepiolite sold under the trade name of 01 by the product of hebei constantu mine limited.

Preparation example 4: (1) adding 0.3kg of carboxymethyl chitosan into 0.9kg of water, and stirring until the carboxymethyl chitosan is completely dissolved to prepare a carboxymethyl chitosan solution;

(2) placing 0.6kg tea saponin, 0.3kg montmorillonite and 0.7kg sepiolite into a nanometer grinding machine, and grinding for 30min to obtain nanometer fine powder;

(3) adding the nanometer fine powder into the carboxymethyl chitosan solution, stirring uniformly, and preparing the composite fiber through wet spinning, wherein the mass ratio of the nanometer fine powder to the carboxymethyl chitosan solution is 0.7: 1.

Preparation example 5: (1) adding 0.5kg of carboxymethyl chitosan into 1.1kg of water, and stirring until the carboxymethyl chitosan is completely dissolved to prepare a carboxymethyl chitosan solution;

(2) placing 0.7kg tea saponin, 0.4kg montmorillonite and 0.8kg sepiolite into a nanometer grinding machine, and grinding for 40min to obtain nanometer fine powder;

(3) adding the nanometer fine powder into the carboxymethyl chitosan solution, stirring uniformly, and preparing the composite fiber through wet spinning, wherein the mass ratio of the nanometer fine powder to the carboxymethyl chitosan solution is 0.8: 1.

Preparation example 6: (1) adding 0.7kg of carboxymethyl chitosan into 1.2kg of water, and stirring until the carboxymethyl chitosan is completely dissolved to prepare a carboxymethyl chitosan solution;

(2) placing 0.8kg tea saponin, 0.5kg montmorillonite and 0.9kg sepiolite into a nanometer grinding machine, and grinding for 50min to obtain nanometer fine powder;

(3) adding the nanometer fine powder into the carboxymethyl chitosan solution, stirring uniformly, and preparing the composite fiber through wet spinning, wherein the mass ratio of the nanometer fine powder to the carboxymethyl chitosan solution is 0.9: 1.