CN113121841A - Inorganic composite guanidine salt polymer antibacterial agent and preparation method thereof - Google Patents
Inorganic composite guanidine salt polymer antibacterial agent and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention discloses an inorganic composite guanidine salt polymer antibacterial agent and a preparation method thereof, wherein the inorganic composite guanidine salt polymer antibacterial agent is prepared by epoxy group functionalized inorganic powder and guanidine salt polymer by taking dimethyl sulfoxide as a reaction solvent, and salicylic acid can be selected as a catalyst; wherein the mass ratio of the inorganic powder to the guanidine salt polymer is 1: 4-10: 1; the salicylic acid accounts for 1-10% of the total mass of the inorganic powder, the guanidine salt polymer and the reaction solvent. The inorganic composite guanidine salt polymer antibacterial agent not only maintains the advantages of the guanidine salt polymer such as thermal stability, high efficiency, broad-spectrum antibacterial property, safety, low toxicity, no stimulation, no generation of bacterial drug resistance, no volatilization, no substances such as heavy metals and phenols, no corrosion to various treated surfaces, and the like, but also has the advantages of dissolution resistance and water washing resistance, and can be directly added into different rubber and plastic materials.
Description
Technical Field
The invention belongs to the field of materials, and relates to an inorganic composite guanidine salt polymer antibacterial agent and a preparation method thereof.
Background
The living environment of human beings has a large number of microorganisms, the types of the microorganisms are various, the microorganisms mainly comprise bacteria, fungi, viruses and the like, and the microorganisms are tiny in shape, fast in propagation, wide in distribution and easy to change. Among them, some microorganisms are harmful to human health and living environment, and thus, there has been a great deal of attention on the research and development of materials for preventing harmful microorganisms, which are environmentally friendly, safe and sanitary, and their applications in products, and controlling the growth and reproduction of harmful microorganisms, in order to obtain a safe and healthy living environment, to reduce the harm of harmful microorganisms to human bodies.
At present, harmful microorganism-resistant materials for inhibiting and destroying harmful microorganisms are mainly natural antibacterial agents, inorganic antibacterial agents and organic antibacterial agents. The natural antibacterial agent is derived from the nature, but is limited by factors such as stability, extraction process, cost and the like, and is limited in industrial application at present. The inorganic antibacterial agent mainly comprises metal and metal oxide, and the inorganic antibacterial agent is mainly prepared by introducing metal ions such as silver, copper, zinc and the like onto inorganic carriers such as phosphate, silicate and the like; the inorganic metal oxide antibacterial agent mainly comprises titanium oxide, magnesium oxide, cuprous oxide and the like, and ceramics are generally used as a carrier; the inorganic antibacterial agent has the main advantages of good heat resistance, but has the defects of higher price, slow antibacterial effect, easy agglomeration in matrix resin and non-compliance of heavy metal silver ions with the national sanitation standard of related food packaging materials.
The organic antibacterial agent mainly comprises quaternary ammonium salts, quaternary phosphonium salts, phenols, pyridines, alcohols, aldehydes, guanidines, imidazoles and the like, is combined with a cytoplasmic membrane of microorganisms to denature proteins and resist metabolism so as to inhibit and kill harmful microorganisms, and can be divided into an organic small-molecular antibacterial agent and an organic high-molecular antibacterial agent according to the molecular structure and molecular weight, wherein the organic small-molecular antibacterial agent has the advantages of high antibacterial efficiency, broad spectrum and the like, but has the defects of poor heat resistance, easy migration and precipitation, no washing resistance, short service life and the like; in recent years, the organic polymer antibacterial agents which are researched more mainly comprise guanidine salt polymers, quaternary ammonium salt polymers, quaternary phosphorus salt polymers, organic tin polymers, chitosan and the like, wherein the antibacterial agent containing the guanidine salt polymers is considered to have great development potential, and the guanidine salt polymers are cationic polyelectrolytes with guanidine salt groups, which mainly form electrostatic adsorption with anions on the surfaces of bacterial cells through cations in molecules to block the action of harmful microbial cell lytic enzymes, so that the cell surface layer structure is deformed to destroy cell membranes, thereby achieving the effects of inhibiting, eliminating and killing microbes; the guanidine salt polymer has the advantages of good water solubility, good photo-thermal stability, high efficiency, broad-spectrum antibacterial property, safety, low toxicity, no stimulation, no generation of bacterial drug resistance, no volatilization, no substances such as heavy metal, phenols and the like, no corrosion to various treated surfaces, environmental friendliness and the like, and is widely applied to medical disinfection and sterilization of foods and other daily necessities. Since guanidyl is a hydrophilic group, most guanidinium polymers have strong water solubility, at present, the guanidinium polymers are mainly used for surface disinfection treatment of products and post-antibacterial finishing of textiles in the form of aqueous solution of the guanidinium polymers, and the guanidinium polymers and plastics or rubber are blended and modified, so that the products gradually lose antibacterial performance due to poor water resistance because the guanidinium polymers are dissolved in water; therefore, it is a very worthy of research to improve the water resistance of the rubber and plastic products containing guanidine salt polymer and maintain the advantages of guanidine salt polymer against harmful microorganisms, and patents CN1445270A, CN106800652A, and CN1569923A describe that guanidine salt polymer and matrix resin molecule are firmly combined together through chemical bonds formed by chemical reaction to prepare antibacterial master batch, and then the antibacterial master batch is used to prepare antibacterial plastics, so that guanidine salt polymer is not easy to run off, thereby endowing the material with durable antibacterial property, however, the mode that the guanidine group-containing polymer is firstly chemically bonded with the matrix resin to prepare the antibacterial master batch and then is added into the rubber and plastic raw material needing antibacterial modification, the type of the matrix resin for preparing the antibacterial master batch can be changed along with the difference of the rubber and plastic raw material needing antibacterial modification, therefore, the prepared antibacterial master batch is required to have strong pertinence, more varieties and brands are required, and the enterprise cost is increased.
Therefore, the harmful microorganism resistant material containing the guanidine salt polymer, which not only retains the advantages of photo-thermal stability, high efficiency, broad-spectrum antibacterial property, safety, low toxicity, no stimulation, no generation of bacterial drug resistance, no volatilization, no substances such as heavy metal, phenols and the like, no corrosion to various treatment surfaces, environmental friendliness and the like of the guanidine salt polymer, but also has the advantages of dissolution resistance and water washing resistance, and can be directly added into different rubber and plastic materials, has important research value and good market prospect.
Disclosure of Invention
The invention aims to solve the problems and provides an inorganic composite guanidine salt polymer antibacterial agent and a preparation method thereof, the inorganic composite guanidine salt polymer antibacterial agent not only maintains the advantages of photo-thermal stability, high-efficiency and broad-spectrum antibacterial property, safety, low toxicity, no stimulation, no generation of bacterial drug resistance, no volatilization, no substances such as heavy metal, phenols and the like, no corrosion to various treatment surfaces, environmental friendliness and the like of a guanidine salt polymer, but also has the advantages of dissolution resistance and water washing resistance, and can be directly added into different rubber and plastic materials.
The purpose of the invention is realized as follows:
the inorganic composite guanidine salt polymer antibacterial agent is prepared by epoxy group functionalized inorganic powder and guanidine salt polymer by taking dimethyl sulfoxide as a reaction solvent, and preferably, salicylic acid is used as a catalyst;
the mass ratio of the inorganic powder to the guanidine salt polymer is 1: 4-10: 1;
the salicylic acid accounts for 1-10% of the total mass of the inorganic powder, the guanidine salt polymer and the reaction solvent.
The epoxy group functionalized inorganic powder in the inorganic composite guanidine salt polymer antibacterial agent is inorganic powder with an epoxy group grafted on the surface of the inorganic powder through a chemical reaction, and the surface of the inorganic powder is chemically modified by adopting an epoxy silane coupling agent, wherein the epoxy silane coupling agent is one or more selected from gamma-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane or 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane.
The inorganic powder in the inorganic composite guanidine salt polymer antibacterial agent is selected from one or more of kieselguhr, attapulgite, montmorillonite, fumed silica, precipitated silica or molecular sieves with the particle size of 10 nm-75 mu m.
The epoxy group functionalized inorganic powder in the inorganic composite guanidine salt polymer antibacterial agent can be burned at a high temperature of more than 600 ℃, and the organic part accounts for 1-30% of the total mass of the epoxy group functionalized inorganic powder.
The guanidine salt polymer in the inorganic composite guanidine salt polymer antibacterial agent is selected from one or more of polyhexamethylene guanidine hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidine propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine phosphate, polyhexamethylene biguanide phosphate, polyhexamethylene guanidine carbonate or polyhexamethylene biguanide carbonate.
The invention also provides a preparation method of the inorganic composite guanidine salt polymer antibacterial agent, which comprises the following steps:
s1: adding epoxy group functionalized inorganic powder and a guanidine salt polymer into a dimethyl sulfoxide solvent, uniformly stirring to form a suspension of epoxy group functionalized inorganic powder, raising the temperature to 50-150 ℃ under the protection of inert gas, keeping the temperature, stirring and reacting for 3-60 hours, and performing chemical grafting reaction modification on the surface of the epoxy group functionalized inorganic powder;
and S2, after the reaction of the step S1 is finished, cooling to room temperature, filtering to separate out a solid product, washing with an organic solvent, washing with distilled water, and drying and crushing the separated solid product.
In the preparation method of the inorganic composite guanidinium polymer antibacterial agent, the inert gas in the step S1 is nitrogen or argon, and the organic solvent in the step S2 is selected from methanol, ethanol or acetone.
In the preparation method of the inorganic composite guanidine salt polymer antibacterial agent, in the step S1, the inorganic powder with functionalized epoxy groups, the guanidine salt polymer and the salicylic acid are added into the dimethyl sulfoxide solvent and uniformly stirred to form a suspension of the inorganic powder with functionalized epoxy groups; the salicylic acid accounts for 1-10% of the total mass of the inorganic powder, the guanidine salt polymer and the reaction solvent.
The inorganic composite guanidine salt polymer antibacterial agent not only maintains the photo-thermal stability, high efficiency and broad-spectrum antibacterial property, safety, low toxicity, no stimulation, no generation of bacterial drug resistance, no volatilization, no substances such as heavy metal, phenols and the like, no corrosion to various treated surfaces, environmental friendliness and the like of the guanidine salt polymer, but also has the advantages of dissolution resistance, water washing resistance and the like, and can be directly added into different rubber and plastic materials.
Detailed Description
The invention discloses an inorganic composite guanidine salt polymer antibacterial agent, which is prepared by using epoxy group functionalized inorganic powder and guanidine salt polymer and dimethyl sulfoxide as a reaction solvent, preferably salicylic acid as a catalyst;
the mass ratio of the inorganic powder to the guanidine salt polymer is 1: 4-10: 1;
the salicylic acid accounts for 1-10% of the total mass of the inorganic powder, the guanidine salt polymer and the reaction solvent.
Wherein the content of the first and second substances,
the epoxy group functionalized inorganic powder is inorganic powder with epoxy groups grafted on the surface of the inorganic powder through chemical reaction, the epoxy silane coupling agent is adopted for surface chemical modification, the surface chemical modification of the inorganic powder adopts a dry process or a wet process, and the inorganic powder is selected from one or more of kieselguhr, attapulgite, montmorillonite, fumed silica, precipitated silica or molecular sieves with the particle size of 10 nm-75 mu m; the epoxy silane coupling agent is selected from one or more of gamma-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane or 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane; the organic part of the epoxy group functionalized inorganic powder can be burned at a high temperature of more than 600 ℃ and accounts for 1 to 30 percent of the total mass of the epoxy group functionalized inorganic powder.
The guanidine salt polymer is selected from one or more of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine nitrate, polyhexamethylene (bis) guanidine phosphate or polyhexamethylene (bis) guanidine carbonate;
the invention also provides a preparation method of the inorganic composite guanidine salt polymer antibacterial agent, which comprises the following steps:
s1: adding epoxy group functionalized inorganic powder and a guanidine salt polymer into a dimethyl sulfoxide solvent, uniformly stirring to form a suspension of epoxy group functionalized inorganic powder, heating to 50-150 ℃ under the protection of inert gas, keeping the temperature, stirring and reacting for 3-60 hours, and performing chemical grafting reaction modification on the surface of the epoxy group functionalized inorganic powder (namely, the guanidine salt polymer with a harmful microorganism resistant functional group is grafted on the surface of the epoxy group functionalized inorganic powder through a chemical bond);
and S2, after the reaction of the step S1 is finished, cooling to room temperature, filtering to separate out a solid product, washing with an organic solvent, washing with distilled water, and drying and crushing the separated solid product.
Further, the inert gas in S1 is nitrogen or argon, and the organic solvent in step S2 is selected from methanol, ethanol, or acetone. Salicylic acid is added into the S1 as a catalyst, and the dosage of the salicylic acid is 1-10% of the total mass of the inorganic powder, the guanidinium polymer and the reaction solvent.
The inorganic composite guanidine salt polymer antibacterial agent prepared by the invention is modified by chemical grafting reaction on the surface of epoxy functionalized inorganic powder, and the guanidine salt polymer with harmful microorganism resistant functional groups is grafted on the surface of the epoxy functionalized inorganic powder through chemical bonds, so that the advantages of the guanidine salt polymer in the aspect of harmful microorganism resistance are retained, meanwhile, the inorganic composite guanidine salt polymer antibacterial agent has the advantages of dissolution resistance and water washing resistance, can be directly added into different rubber and plastic materials, and can be applied to the fields of harmful microorganism resistant plastics, rubber, fibers, films or coatings with higher requirements on water resistance, and the like.
The present invention will be further described with reference to examples 1 to 2.
Example 1
Adding 100g of fumed silica subjected to 120 ℃ and pre-drying treatment for 5 hours into 3000ml of absolute ethyl alcohol aqueous solution (the mass ratio of absolute ethyl alcohol to distilled water is 3:1), adjusting the pH value to 4-5 by using hydrochloric acid, starting stirring and assisting an ultrasonic environment to uniformly disperse the anhydrous ethyl alcohol aqueous solution for 30min, slowly dropping 20g of gamma-glycidyl ether oxypropyl trimethoxysilane (CAS number: 2530-83-8), heating to 70 ℃, stirring at a constant temperature for 10 hours, carrying out suction filtration on a white carbon black suspension, washing 3 times by using absolute ethyl alcohol, drying and grinding to obtain epoxy group functionalized white carbon black, storing for later use, sampling, carrying out 600 ℃ and 5 hours high temperature test, and obtaining a weight loss rate of 10.2%;
adding 50g of the prepared epoxy group functionalized white carbon black, 10g of polyhexamethylene guanidine hydrochloride (average molecular weight 10000) and 20g of salicylic acid into 400 ml of dimethyl sulfoxide solvent, stirring under the protection of argon gas, assisting an ultrasonic environment to uniformly disperse the mixture for 30min, heating to 80 ℃ under the protection of argon gas, stirring at a constant temperature for 24 hours, carrying out suction filtration on the suspension, washing with absolute ethyl alcohol for 3 times, washing with distilled water for 3 times, and drying and crushing the separated solid product to obtain the sample 1 of the example 1.
Example 2:
placing diatomite (with the average particle size of 20 microns) at 250 ℃ for pretreatment for 4 hours, cooling to room temperature, weighing 100g of diatomite, adding the diatomite into 1000ml of absolute ethyl alcohol/water (volume ratio is 1:1), dropwise adding a dilute acetic acid solution to enable the pH value of a mixed solution to be 4-5, starting stirring and assisting an ultrasonic environment to uniformly disperse the mixed solution for 30 minutes, gradually dropwise adding 30g of gamma-glycidyl ether oxypropyl triethoxysilane (CAS number: 2602-34-8), heating to 70 ℃, stirring at constant temperature for 10 hours, carrying out suction filtration on the diatomite suspension, cleaning 3 times with absolute ethyl alcohol, drying and grinding to obtain epoxy group functionalized diatomite for storage, sampling, and placing at 600 ℃ for 5 hours to test the weight loss rate to be 7.3%.
Adding 50g of the prepared epoxy group functionalized diatomite, 10g of polyhexamethylene guanidine hydrochloride (average molecular weight 10000) and 20g of salicylic acid into 400 ml of dimethyl sulfoxide solvent, heating to 70 ℃ under the protection of argon, stirring at constant temperature for 45 hours, carrying out suction filtration on the suspension, washing with absolute ethyl alcohol for 3 times, washing with distilled water for 3 times, drying and crushing the separated solid product, and thus obtaining a sample 2 in example 2.
The test standard of the embodiment 1-2 adopts a GB/T31402-2015 plastic surface antibacterial performance test method, and the bacteria for detection: staphylococcus aureus (ATCC 6538P), Escherichia coli (ATCC 8739), Candida albicans (ATCC 10231).
Preparation of antimicrobial polypropylene of example 1:
the preparation method comprises the steps of fully and uniformly stirring a sample 1 of 2000g of polypropylene (with a melt index of 25g/10min), 1.25g of antioxidant 1010, 1.25g of antioxidant 168 and 223g, feeding the mixture into a double-screw extruder for melt blending, extruding and granulating at the temperature of 190-220 ℃ and the rotating speed of 400rpm, drying the extruded granules at the constant temperature of 90 ℃ for 9 hours, injecting the granules at the injection temperature of 200-220 ℃ to form a polypropylene sample of 50mm x 50mm 3mm, placing the polypropylene sample in a Soxhlet extractor, extracting the polypropylene sample for 72 hours by using water as a solvent, and then carrying out an antibacterial test.
Preparation of antimicrobial polypropylene of example 2:
fully and uniformly stirring a sample 2 of 2000g of polypropylene (with a melt index of 25g/10min), 1.25g of antioxidant 1010, 1.25g of antioxidant 168 and 325g, feeding the mixture into a double-screw extruder for melt blending, extruding and granulating at the temperature of 190-220 ℃ and the rotating speed of 400rpm, drying the extruded granules at the constant temperature of 90 ℃ for 9 hours, injecting the granules into a polypropylene sample of 50mm x 50mm 3mm at the injection temperature of 200-220 ℃, placing the polypropylene sample into a Soxhlet extractor, extracting the polypropylene sample for 72 hours by using water as a solvent, and then carrying out an antibacterial test.
The results of the performance tests for examples 1-2 are shown in Table 1:
TABLE 1 results of Performance test of examples 1-2
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (10)
1. The inorganic composite guanidine salt polymer antibacterial agent is characterized by being prepared from inorganic powder with functionalized epoxy groups and a guanidine salt polymer by taking dimethyl sulfoxide as a reaction solvent;
the mass ratio of the inorganic powder to the guanidine salt polymer is 1: 4-10: 1.
2. The inorganic composite guanidine salt polymer antibacterial agent according to claim 1, further comprising salicylic acid as a catalyst, wherein the salicylic acid accounts for 1-10% of the total mass of the inorganic powder, the guanidine salt polymer and the reaction solvent.
3. The inorganic composite guanidine salt polymer antibacterial agent of claim 1, wherein the epoxy group functionalized inorganic powder is obtained by grafting epoxy groups on the surface of inorganic powder through a chemical reaction.
4. The inorganic composite guanidinium polymer antibacterial agent of claim 3, wherein the inorganic powder chemically modified with the epoxy silane coupling agent surface.
5. The inorganic composite guanidinium polymer antibacterial agent of claim 4, wherein the epoxysilane coupling agent is selected from one or more of gamma-glycidoxypropyltrimethoxysilane, 3- (2, 3-glycidoxy) propylmethyldimethoxysilane, gamma-glycidoxypropyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltriethoxysilane, beta- (3, 4-epoxycyclohexyl) -ethyltrimethoxysilane, or 3- (2, 3-glycidoxy) propylmethyldiethoxysilane.
6. The inorganic composite guanidine salt polymer antibacterial agent of any one of claims 1 to 5, wherein the inorganic powder is selected from one or more of diatomite, attapulgite, montmorillonite, fumed silica, precipitated silica or molecular sieve with a particle size of 10nm to 75 μm, and/or,
the organic part of the epoxy group functionalized inorganic powder can be burned at a high temperature of more than 600 ℃ and accounts for 1 to 30 percent of the total mass of the epoxy group functionalized inorganic powder.
7. The inorganic complex guanidinium polymer antimicrobial of claim 1, wherein the guanidinium polymer is selected from one or more of polyhexamethylene guanidinium hydrochloride, polyhexamethylene biguanide hydrochloride, polyhexamethylene guanidium propionate, polyhexamethylene biguanide propionate, polyhexamethylene guanidine nitrate, polyhexamethylene biguanide nitrate, polyhexamethylene guanidine phosphate, polyhexamethylene biguanide phosphate, polyhexamethylene guanidine carbonate, or polyhexamethylene biguanide carbonate.
8. A method for preparing the inorganic complex guanidinium polymer antibacterial agent of claim 1, comprising the steps of:
s1: adding epoxy group functionalized inorganic powder and a guanidine salt polymer into a dimethyl sulfoxide solvent, uniformly stirring to form a suspension of epoxy group functionalized inorganic powder, heating to 50-150 ℃ under the protection of inert gas, keeping the reaction temperature, stirring and reacting for 3-60 hours, and performing chemical grafting reaction modification on the surface of the epoxy group functionalized inorganic powder;
and S2, after the reaction of the step S1 is finished, cooling to room temperature, filtering to separate out a solid product, washing with an organic solvent, washing with distilled water, and drying and crushing the separated solid product.
9. The method of claim 8, wherein the inert gas is nitrogen or argon in step S1, and the organic solvent is selected from methanol, ethanol, and acetone in step S2.
10. The method of claim 8, wherein in step S1, the epoxy-functionalized inorganic powder, the guanidinium polymer, and the salicylic acid are added to the dimethylsulfoxide solvent and stirred uniformly to form a suspension of the epoxy-functionalized inorganic powder;
the salicylic acid accounts for 1-10% of the total mass of the inorganic powder, the guanidine salt polymer and the reaction solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115948032A (en) * | 2022-11-30 | 2023-04-11 | 广东省科学院生物与医学工程研究所 | Biodegradable slow-release antibacterial preservative film and preparation method and application thereof |
| CN117264161A (en) * | 2023-11-17 | 2023-12-22 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of bio-based blocked isocyanate cross-linking agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919554A (en) * | 1998-01-30 | 1999-07-06 | Microban Products Company | Antimicrobial fiberglass reinforced plastic composite |
| CN110128667A (en) * | 2019-05-21 | 2019-08-16 | 华东理工大学 | Polyolefin antibacterial matrices and its preparation and the application for being used to prepare antibacterial condensation polymer |
| CN110313470A (en) * | 2019-07-04 | 2019-10-11 | 安徽大学 | A kind of preparation method of grafted guanidine salt polymer hollow mesoporous silicon oxide antibacterial agent |
-
2021
- 2021-04-21 CN CN202110431861.5A patent/CN113121841A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5919554A (en) * | 1998-01-30 | 1999-07-06 | Microban Products Company | Antimicrobial fiberglass reinforced plastic composite |
| CN110128667A (en) * | 2019-05-21 | 2019-08-16 | 华东理工大学 | Polyolefin antibacterial matrices and its preparation and the application for being used to prepare antibacterial condensation polymer |
| CN110313470A (en) * | 2019-07-04 | 2019-10-11 | 安徽大学 | A kind of preparation method of grafted guanidine salt polymer hollow mesoporous silicon oxide antibacterial agent |
Non-Patent Citations (1)
| Title |
|---|
| 王涛: "胍盐类抗菌高分子复合材料的制备与性能研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》（月刊）》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115948032A (en) * | 2022-11-30 | 2023-04-11 | 广东省科学院生物与医学工程研究所 | Biodegradable slow-release antibacterial preservative film and preparation method and application thereof |
| CN117264161A (en) * | 2023-11-17 | 2023-12-22 | 江苏瑞洋安泰新材料科技有限公司 | Preparation method of bio-based blocked isocyanate cross-linking agent |
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