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CN-116554407-B - Guanidine-containing antibacterial polymer, preparation method and application thereof

CN116554407BCN 116554407 BCN116554407 BCN 116554407BCN-116554407-B

Abstract

The application provides a guanidine group-containing antibacterial polymer, a preparation method and application thereof. The nanofiber membrane prepared from the guanidine-containing antibacterial polymer has good filtering effect on PM in air, and has good antibacterial effect on staphylococcus aureus and escherichia coli even when stored for a long time.

Inventors

  • ZHAO XINGLEI
  • JIANG PAN
  • HUA TING
  • WANG PENG

Assignees

  • 嘉兴富瑞邦新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20230526

Claims (9)

  1. 1. The preparation of the guanidine-containing antibacterial polymer is characterized by comprising the following steps: (1) Adding acrylic monomers and styrene monomers into volatile organic solvents, uniformly mixing, and then adding an initiator BPO and an organic polymer chain transfer agent shown in the formulas II-C to prepare a mixed solution; (2) Adding volatile organic solvent into a reaction bottle, heating to 80-100 ℃, dropwise adding the mixed solution obtained in the step (1) for 2-6 hours, carrying out heat preservation reaction for 2-4 hours after the dropwise adding is finished, and carrying out aftertreatment to obtain the guanidino-containing antibacterial polymer; II-C; Wherein R 1 represents a formyl group, an acetyl group, a substituted or unsubstituted aryl group or a carboxyl group having 1 to 5 carbon atoms; x and y are integers, and x and y are 3 (1-3).
  2. 2. The antibacterial polymer containing guanidine groups of claim 1, wherein the aryl group substituted in R 1 is Wherein R 5 represents hydrogen, methyl or ethyl.
  3. 3. The method for producing a guanidine group-containing antibacterial polymer according to any one of claims 1 to 2, comprising the steps of: (1) Adding acrylic monomers and styrene monomers into volatile organic solvents, uniformly mixing, and then adding an initiator BPO and an organic polymer chain transfer agent shown in the formulas II-C to prepare a mixed solution; (2) Adding volatile organic solvent into a reaction bottle, heating to 80-100 ℃, dropwise adding the mixed solution obtained in the step (1) for 2-6 hours, carrying out heat preservation reaction for 2-4 hours after the dropwise adding is finished, and carrying out aftertreatment to obtain the guanidino-containing antibacterial polymer; II-C。
  4. 4. the method for preparing a guanidine group-containing antibacterial polymer according to claim 3, wherein the method for preparing the organic polymer chain transfer agent comprises the following steps: Adding hydroxyethyl acrylate and polymerizable guanidyl monomer into ethyl acetate, uniformly mixing, and adding a thermal initiator after uniformly mixing to prepare a mixed solution; (1.2) adding ethyl acetate into a reaction bottle, heating the ethyl acetate in the reaction bottle to 60-80 ℃, starting to dropwise add the mixed solution in the step (1.1) for 2-6 hours, carrying out heat preservation reaction for 2-4 hours after the dropwise addition is finished, and carrying out aftertreatment to obtain the organic polymer; (1.3) adding the organic polymer obtained in the step (1.2) into an ether organic solvent, continuously adding a catalyst, potassium carbonate, water and 4-mercaptophenylboronic acid to react at 70-90 ℃ to obtain an organic polymer chain transfer agent, wherein the polymerizable guanidino monomer represents 。
  5. 5. The method for preparing a guanidine group-containing antibacterial polymer according to claim 4, wherein the method for preparing the thermal initiator comprises the following steps: Dissolving sodium dodecyl benzene sulfonate and sodium carbonate in water, mixing uniformly at room temperature, adding 25-40% hydrogen peroxide solution, dropwise adding 3-bromobenzoyl chloride, heating to 30-40 ℃ after the dropwise adding is finished, and carrying out post-treatment after the reaction is finished to obtain the thermal initiator.
  6. 6. The method for preparing a guanidine group-containing antibacterial polymer according to claim 4, wherein the method for preparing the polymerizable guanidine group monomer comprises the following steps: adding a guanidino monomer and triethylamine into a low-boiling point organic solvent, cooling the system to-10-0 ℃, dropwise adding acryloyl chloride, reacting for 2-4 hours after the dropwise adding is finished, and performing aftertreatment after the reaction is finished to obtain a polymerizable guanidino monomer; wherein the guanidino monomer represents 。
  7. 7. The method for preparing a guanidine group-containing antibacterial polymer according to claim 4, wherein the catalyst is a palladium catalyst.
  8. 8. Use of a guanidine-containing antimicrobial polymer according to any one of claims 1-2 for the preparation of an antimicrobial agent.
  9. 9. The method of claim 8, wherein the antimicrobial agent is used for preparing an antimicrobial nanofiber membrane.

Description

Guanidine-containing antibacterial polymer, preparation method and application thereof Technical Field The invention belongs to the field of organic synthesis, and particularly relates to a guanidine-containing antibacterial polymer, a preparation method and application thereof. Background The electrostatic spinning nanofiber refers to a nanofiber with a diameter of nanometer grade, which is obtained by adding electrostatic voltage to a polymer solution, stretching the polymer solution in a very short time and a certain distance under the action of the electric field force of the electrostatic voltage, volatilizing a solvent, and finally on a grounded receiving polar plate. The method can be used for preparing most polymer nanofibers, such as PVA, PVP, PAN, PVDF, PES, PS, PU and the like, and the prepared fibers have different morphologies and wide application fields, wherein the nanofiber membrane has good particle blocking property (particle pollutants in air such as fine particles, carbon dioxide, sulfur dioxide and the like can be effectively filtered), high specific surface area, good adsorptivity and the like, and the electrospun nanofiber is also widely applied to the filtration field. However, the electrostatic spinning nanofiber in the prior art is spun from high polymers, can only intercept and electrostatically adsorb suspended particles in the air, and cannot remove bacteria, viruses and organic pollutants in the air. Under the guidance of the background and application requirements, development of nanofiber filter materials with an antibacterial function is started, for example, chinese patent document CN102302875A discloses a preparation method of an antibacterial air filter membrane, wherein an inorganic antibacterial agent containing metal or an organic antibacterial agent containing sulfur and bromine, a polymer, an additive and a solvent are blended into a solution, or the antibacterial agent and the polymer are subjected to melt blending to obtain a uniform melt, and then the blend solution or the melt is subjected to electrostatic spinning to spin nanofibers on the surface of a non-woven fabric to obtain the antibacterial air filter membrane. Aiming at the problems existing in the prior art, how to provide a guanidine-containing antibacterial polymer with good filtering effect and antibacterial performance and good antibacterial performance when used for a long time is a problem to be solved in the invention. Disclosure of Invention The invention aims to provide a guanidine-containing antibacterial polymer, a preparation method and application thereof, so as to solve the problems in the background art. In order to achieve the above purpose, the invention provides the following technical scheme that in one aspect, the invention provides a guanidine group-containing antibacterial polymer, which has a structure shown in the following formula I: Wherein R 1 represents formyl, acetyl, substituted or unsubstituted aryl or carboxyl containing 1 to 5 carbon atoms, R 2 and R 3 each independently represent hydrogen, hydroxy or methyl, R 4 represents benzyl, phenyl, biphenyl, linear or branched alkyl containing 1 to 8 carbon atoms; x, y, a, b are integers, and x: y is 3 (1-3), a is 30-100, and b is 20-80. As a further improvement, the substituted or unsubstituted aryl group in R 1 isWherein R 5 represents hydrogen, methyl or ethyl. As a further improvement, the guanidine-containing antimicrobial polymer is selected from the group consisting of compounds represented by the following formulas I-1 to I-3: Wherein R 4 represents a linear or branched alkyl group having 1 to 8 carbon atoms. In another aspect, the present invention provides a method for preparing a guanidine group-containing antimicrobial polymer, comprising the steps of: (1) Adding acrylic monomers and styrene monomers into volatile organic solvents, uniformly mixing, and then adding an initiator BPO and an organic polymer chain transfer agent shown in the formulas II-C to prepare a mixed solution; (2) Adding volatile organic solvent into a reaction bottle, heating to 80-100 ℃, dropwise adding the mixed solution obtained in the step (1) for 2-6 hours, carrying out heat preservation reaction for 2-4 hours after the dropwise adding is finished, and carrying out aftertreatment to obtain the guanidino-containing antibacterial polymer; as a further improvement, the styrene-based monomer is styrene, methyl styrene, p-hydroxystyrene or the like. As a further improvement, the method for preparing the organic polymer chain transfer agent comprises the following steps: Adding hydroxyethyl acrylate and polymerizable guanidyl monomer into ethyl acetate, uniformly mixing, and adding a thermal initiator after uniformly mixing to prepare a mixed solution; (1.2) adding ethyl acetate into a reaction bottle, heating the ethyl acetate in the reaction bottle to 60-80 ℃, starting to dropwise add the mixed solution in the step (1.1) for 2-6 hours, carrying ou