阅读说明：本技术 一种抗菌性壳聚糖-纤维素的生物质复合薄膜的制法和应用 (Preparation method and application of antibacterial chitosan-cellulose biomass composite film ) 是由 潘红蓉 于 2020-12-30 设计创作，主要内容包括：本发明涉及抗菌材料技术领域,且公开了一种抗菌性壳聚糖-纤维素的生物质复合薄膜,在N-羟基丁二酰亚胺和二环己基碳化二亚胺的活化作用下,使叠氮乙酸与壳聚糖进行酰胺化反应,得到叠氮化壳聚糖,基于叠氮-炔点击反应的原理,在溴化亚铜和三乙胺配位和催化作用下,使壳聚糖的叠氮基团与2-炔丙基四甲基胍的炔基发生点击反应,得到四甲基胍基壳聚糖作为活性抗菌剂,聚乙烯醇具有良好的成膜性和阻隔性,丙三醇具有增塑效果,而壳聚糖与纤维素的相容性非常好,从而使四甲基胍基壳聚糖作为抗菌剂与纳米纤维素复合成膜,得到抗菌性壳聚糖-纤维素的生物质复合薄膜,具有优异的抗菌活性和抑菌效果。(The invention relates to the technical field of antibacterial materials, and discloses an antibacterial chitosan-cellulose biomass composite film, wherein azido acetic acid and chitosan are subjected to amidation reaction under the activation action of N-hydroxysuccinimide and dicyclohexylcarbodiimide to obtain azido chitosan, under the coordination and catalysis action of cuprous bromide and triethylamine, azido groups of the chitosan and alkynyl of 2-propargyl tetramethylguanidine are subjected to click reaction to obtain tetramethylguanidino chitosan as an active antibacterial agent, polyvinyl alcohol has good film forming property and barrier property, glycerol has a plasticizing effect, the compatibility of the chitosan and cellulose is very good, thus the tetramethylguanidino chitosan as an antibacterial agent is compounded with nano-cellulose to form a film, and the chitosan-cellulose biomass composite antibacterial film is obtained, has excellent antibacterial activity and bacteriostatic effect.)

1. An antibacterial chitosan-cellulose biomass composite film is characterized in that: the preparation method of the antibacterial chitosan-cellulose biomass composite film comprises the following steps:

(1) adding ethyl acetate solvent and tetramethyl guanidine into a conical flask, slowly dropwise adding ethyl acetate solution of bromopropyne, placing in a constant temperature water bath device, reacting at constant temperature, distilling under reduced pressure, extracting and purifying to obtain the compound with molecular formula C₁₀H₁₄N2-propargyl tetramethylguanidine;

(2) adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 6-12h, adding azidoacetic acid, a catalyst and a condensing agent, reacting at constant temperature in a dark place, precipitating, filtering, and washing to obtain azido chitosan;

(3) adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 6-12h, adding 2-propargyl tetramethylguanidine, a catalyst and a ligand, reacting at a constant temperature of 20-40 ℃ for 24-48h under the protection of nitrogen, precipitating, filtering, and washing to obtain tetramethylguanidino chitosan;

(4) adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 30-60min, adding nanocellulose and glycerol serving as a plasticizer, uniformly dispersing by ultrasonic wave, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film, which is used in the field of antibacterial film materials.

2. The antibacterial chitosan-cellulose biomass composite film according to claim 1, wherein: the thermostatic water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected to the lower portion of the water bath tank, a conical flask is arranged above the heat-conducting plate, the lower portion of the heat-conducting plate is fixedly connected with a heating plate, a heat-insulating sleeve is fixedly connected to the outer side of the water bath tank, the upper portion of the heat-insulating sleeve is fixedly connected with a screw, an adjusting gear is movably connected with the screw, and the adjusting gear is movably connected with an upper.

3. The antibacterial chitosan-cellulose biomass composite film according to claim 1, wherein: the catalyst in the step (2) is N-hydroxysuccinimide, the condensing agent is dicyclohexylcarbodiimide, and the mass ratio of the chitosan to the azidoacetic acid to the N-hydroxysuccinimide to the dicyclohexylcarbodiimide is 100:10-30:35-100: 60-180.

4. The antibacterial chitosan-cellulose biomass composite film according to claim 1, wherein: the catalyst in the step (3) is cuprous bromide and the ligand is triethylamine, wherein the mass ratio of the chitosan azide to the 2-propargyl tetramethylguanidine to the cuprous bromide to the triethylamine is 100:15-50:0.05-0.1: 0.08-0.15.

5. The antibacterial chitosan-cellulose biomass composite film according to claim 1, wherein: the mass ratio of the polyvinyl alcohol, the tetramethyl guanidine chitosan, the nano cellulose and the glycerol in the step (4) is 15-30:30-80:100: 15-25.

Technical Field

The invention relates to the technical field of antibacterial materials, in particular to a preparation method and application of an antibacterial chitosan-cellulose biomass composite film.

Background

The existing antibacterial material is prepared by adding an antibacterial agent with antibacterial activity into a high polymer material to prepare antibacterial plastic, antibacterial fiber, an antibacterial coating and the like, wherein the traditional antibacterial agent is an inorganic antibacterial agent such as nano silver, zinc oxide, titanium dioxide and the like; and organic antibacterial agents such as anilide compounds, quaternary ammonium salt compounds, biguanidine compounds, and phenol compounds.

The biguanidine compounds such as pentamethylguanidine, 1- (3-chloro-4-heptyloxyphenyl) biguanide and the like are used as unitary organic alkali, and guanidine agents form stable cations after receiving protons and can be combined with phosphate walls in bacterial cell walls, so that the growth and division of microorganisms such as bacteria and the like, the plumule germination process and the cell wall structure are influenced, and the effect of inhibiting or killing the microorganisms is achieved, and the biguanidine compounds are organic antibacterial agents with excellent antibacterial performance.

Cellulose is a polysaccharide compound which is widely distributed and contains most of cellulose in nature, has rich sources and good biocompatibility and biodegradability, is widely applied to the aspects of water pollution adsorption, air purification, antibacterial materials, packaging materials, medical supplies and the like, and needs to be modified by adding a material with good compatibility with the cellulose in order to further improve the comprehensive properties of the cellulose material such as antibacterial property and the like so as to meet the requirements of production and life and the rapid development of industry.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides a preparation method and application of an antibacterial chitosan-cellulose biomass composite film, and solves the problems that cellulose film materials do not have antibacterial performance and limit the practical application of cellulose.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the antibacterial chitosan-cellulose biomass composite film comprises the following steps:

(1) adding ethyl acetate solvent into the conical flaskAdding tetramethylguanidine, slowly dropwise adding ethyl acetate solution of bromopropyne, placing in constant temperature water bath device, reacting at 15-35 deg.C for 12-24 hr, distilling under reduced pressure to remove solution, adding dichloromethane and saturated saline solution, extracting and purifying, vacuum filtering dichloromethane organic phase to obtain compound C₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 6-12h, adding azidoacetic acid, a catalyst and a condensing agent, reacting for 12-36h at constant temperature and in a dark place at 40-60 ℃, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 6-12h, adding 2-propargyl tetramethylguanidine, a catalyst and a ligand, reacting at a constant temperature of 20-40 ℃ for 24-48h under the protection of nitrogen, adding distilled water for precipitation, filtering off the solvent, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 30-60min, adding nanocellulose and glycerol serving as a plasticizer, uniformly dispersing by ultrasonic wave, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film, which is used in the field of antibacterial film materials.

Preferably, the thermostatic water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected to the lower portion of the water bath tank, a conical flask is arranged on the upper portion of the heat-conducting plate, the lower portion of the heat-conducting plate is fixedly connected with a heating plate, a heat-insulating sleeve is fixedly connected to the outer side of the water bath tank, the upper portion of the heat-insulating sleeve is fixedly connected with a screw, an adjusting gear is movably connected with the screw, and the adjusting gear is movably connected.

Preferably, the catalyst in the step (2) is N-hydroxysuccinimide, the condensing agent is dicyclohexylcarbodiimide, and the mass ratio of the chitosan to the azidoacetic acid to the N-hydroxysuccinimide to the dicyclohexylcarbodiimide is 100:10-30:35-100: 60-180.

Preferably, the catalyst in the step (3) is cuprous bromide, and the ligand is triethylamine, wherein the mass ratio of the chitosan azide to the 2-propargyl tetramethylguanidine to the cuprous bromide to the triethylamine is 100:15-50:0.05-0.1: 0.08-0.15.

Preferably, the mass ratio of the polyvinyl alcohol, the tetramethyl guanidine chitosan, the nano cellulose and the glycerol in the step (4) is 15-30:30-80:100: 15-25.

Drawings

FIG. 1 is a schematic structural view of a thermostatic waterbath device;

FIG. 2 is a schematic top view of the upper insulation layer;

FIG. 3 is a chemical structural formula of 2-propargyl tetramethylguanidine.

1-a constant temperature water bath device; 2-water bath; 3-heat conducting plate; 4-a conical flask; 5-heating a sheet; 6-insulating sleeve; 7-a screw; 8-adjusting the gear; 9-upper heat-insulating layer.

(III) advantageous technical effects

Compared with the prior art, the invention has the following chemical experiment principle and beneficial technical effects:

according to the antibacterial chitosan-cellulose biomass composite film, under the activation action of N-hydroxysuccinimide and dicyclohexylcarbodiimide, carboxyl of azido acetic acid and amino of chitosan are subjected to amidation reaction to obtain azido chitosan, so that an azido matrix is introduced into a molecular chain of the chitosan, and based on the principle of azido-alkyne click reaction, under the coordination and catalysis of cuprous bromide and triethylamine, an azido group of the chitosan and an alkynyl of 2-propargyl tetramethylguanidine are subjected to click reaction to obtain tetramethylguanidino chitosan, so that an antibacterial active group is introduced into the molecular chain of the chitosan and serves as an active antibacterial agent.

According to the antibacterial chitosan-cellulose biomass composite film, polyvinyl alcohol has good film forming property and barrier property, glycerol has a plasticizing effect, and chitosan and cellulose have good compatibility, so that tetramethyl guanidino chitosan serving as an antibacterial agent is compounded with nanocellulose to form a film, the antibacterial chitosan-cellulose biomass composite film is obtained, and the cellulose film material is endowed with excellent antibacterial activity and antibacterial effect.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: the preparation method of the antibacterial chitosan-cellulose biomass composite film comprises the following steps:

(1) adding an ethyl acetate solvent and tetramethylguanidine into a conical flask, slowly dropwise adding an ethyl acetate solution of bromopropyne, and placing the mixture into a constant-temperature water bath device, wherein the constant-temperature water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected below the water bath tank, the conical flask is arranged above the heat-conducting plate, the lower part of the heat-conducting plate is fixedly connected with a heating plate, the outer side of the water bath tank is fixedly connected with a heat-insulating sleeve, the upper part of the heat-insulating sleeve is fixedly connected with a screw, the screw is movably connected with an adjusting gear, the adjusting gear is movably connected with an upper heat-insulating layer, the mixture is subjected to constant-temperature reaction at 15-35 ℃ for 12-24h, the solution is removed by reduced-pressure₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 6-12h, adding azidoacetic acid, a catalyst N-hydroxysuccinimide and a condensing agent dicyclohexylcarbodiimide in a mass ratio of 100:10-30:35-100:60-180, reacting for 12-36h at a constant temperature of 40-60 ℃ in a dark place, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 6-12h, adding 2-propargyl tetramethylguanidine, a catalyst cuprous bromide and a ligand triethylamine, wherein the mass ratio of the four substances is 100:15-50:0.05-0.1:0.08-0.15, reacting at a constant temperature of 20-40 ℃ for 24-48h under the protection of nitrogen, adding distilled water for precipitation, filtering to remove the solvent, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 30-60min, adding nanocellulose and glycerol serving as a plasticizer, wherein the mass ratio of the four substances is 15-30:30-80:100:15-25, uniformly dispersing by ultrasonic, then carrying out vacuum defoaming on the solution, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film, wherein the antibacterial chitosan-cellulose biomass composite film is used in the field of antibacterial film materials.

Example 1

(1) Adding an ethyl acetate solvent and tetramethylguanidine into a conical flask, slowly dropwise adding an ethyl acetate solution of bromopropyne, and placing the solution into a constant-temperature water bath device, wherein the constant-temperature water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected below the water bath tank, the conical flask is arranged above the heat-conducting plate, the lower part of the heat-conducting plate is fixedly connected with a heating plate, a heat-insulating sleeve is fixedly connected outside the water bath tank, the upper part of the heat-insulating sleeve is fixedly connected with a screw, the screw is movably connected with an adjusting gear, the adjusting gear is movably connected with an upper heat-insulating layer, the solution is removed by reduced pressure distillation at the constant temperature of 15 ℃ for 12 hours, dichloromethane and saturated saline solution are added for extraction₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 6h, adding azidoacetic acid, a catalyst N-hydroxysuccinimide and a condensing agent dicyclohexylcarbodiimide in a mass ratio of 100:10:35:60, reacting at constant temperature and in a dark place at 40 ℃ for 12h, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 6 hours, adding 2-propargyl tetramethylguanidine, a catalyst cuprous bromide and a ligand triethylamine, wherein the mass ratio of the four substances is 100:15:0.05:0.08, reacting for 24 hours at a constant temperature of 20 ℃ under the protection of nitrogen, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 30min, adding nanocellulose and glycerol serving as a plasticizer, wherein the mass ratio of the nanocellulose to the glycerol is 15:30:100:15, ultrasonically dispersing uniformly, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film.

Example 2

(1) Adding an ethyl acetate solvent and tetramethylguanidine into a conical flask, slowly dropwise adding an ethyl acetate solution of bromopropyne, and placing the solution into a constant-temperature water bath device, wherein the constant-temperature water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected below the water bath tank, the conical flask is arranged above the heat-conducting plate, the heat-conducting plate is fixedly connected below the heat-conducting plate, a heat-insulating sleeve is fixedly connected outside the water bath tank, the heat-insulating sleeve is fixedly connected above a screw, the screw is movably connected with an adjusting gear, the adjusting gear is movably connected with an upper heat-insulating layer, the solution is removed by reduced pressure distillation at the constant temperature of 35 ℃ for 18 hours, dichloromethane and saturated saline solution are added, extraction and purification are carried out₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 12h, adding azidoacetic acid, a catalyst N-hydroxysuccinimide and a condensing agent dicyclohexylcarbodiimide in a mass ratio of 100:15:55:100, reacting for 36h at a constant temperature of 50 ℃ in a dark place, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 6 hours, adding 2-propargyl tetramethylguanidine, a catalyst cuprous bromide and a ligand triethylamine, wherein the mass ratio of the four substances is 100:25:0.06:0.1, reacting for 48 hours at a constant temperature of 30 ℃ under the protection of nitrogen, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 60min, adding nanocellulose and glycerol serving as a plasticizer, wherein the mass ratio of the nanocellulose to the glycerol is 20:40:100:18, ultrasonically dispersing uniformly, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film.

Example 3

(1) Adding an ethyl acetate solvent and tetramethylguanidine into a conical flask, slowly dropwise adding an ethyl acetate solution of bromopropyne, and placing the solution into a constant-temperature water bath device, wherein the constant-temperature water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected below the water bath tank, the conical flask is arranged above the heat-conducting plate, the lower part of the heat-conducting plate is fixedly connected with a heating plate, a heat-insulating sleeve is fixedly connected outside the water bath tank, the upper part of the heat-insulating sleeve is fixedly connected with a screw, the screw is movably connected with an adjusting gear, the adjusting gear is movably connected with an upper heat-insulating layer, reacting at the constant temperature of 25 ℃ for 18 hours, distilling under reduced pressure to remove the solution, adding dichloromethane and saturated saline solution₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 10h, adding azidoacetic acid, a catalyst N-hydroxysuccinimide and a condensing agent dicyclohexylcarbodiimide in a mass ratio of 100:22:80:140, reacting at a constant temperature of 50 ℃ in a dark place for 24h, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 10 hours, adding 2-propargyl tetramethylguanidine, a catalyst cuprous bromide and a ligand triethylamine, wherein the mass ratio of the four substances is 100:38:0.08:0.12, reacting for 36 hours at a constant temperature of 30 ℃ under the protection of nitrogen, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidino chitosan into a conical flask, stirring for 50min, adding nanocellulose and plasticizer glycerol, wherein the mass ratio of the nanocellulose to the plasticizer glycerol is 25:60:100:22, ultrasonically dispersing uniformly, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film.

Example 4

(1) Adding an ethyl acetate solvent and tetramethylguanidine into a conical flask, slowly dropwise adding an ethyl acetate solution of bromopropyne, and placing the solution into a constant-temperature water bath device, wherein the constant-temperature water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected below the water bath tank, the conical flask is arranged above the heat-conducting plate, the heat-conducting plate is fixedly connected below the heat-conducting plate, a heat-insulating sleeve is fixedly connected outside the water bath tank, the heat-insulating sleeve is fixedly connected above a screw, the screw is movably connected with an adjusting gear, the adjusting gear is movably connected with an upper heat-insulating layer, the solution is removed by reduced pressure distillation at the constant temperature of 35 ℃ for 24 hours, dichloromethane and saturated saline solution are added, extraction and purification are carried out₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 12h, adding azidoacetic acid, a catalyst N-hydroxysuccinimide and a condensing agent dicyclohexylcarbodiimide in a mass ratio of 100:30:100:180, reacting for 36h at a constant temperature of 60 ℃ in a dark place, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 12h, adding 2-propargyl tetramethylguanidine, a catalyst cuprous bromide and a ligand triethylamine, wherein the mass ratio of the four substances is 100:50:0.1:0.15, reacting at a constant temperature of 40 ℃ for 48h under the protection of nitrogen, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 60min, adding nanocellulose and glycerol serving as a plasticizer, wherein the mass ratio of the nanocellulose to the glycerol is 30:80:100:25, ultrasonically dispersing uniformly, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film.

Comparative example 1

(1) Adding ethyl acetate solvent and tetraMethyl guanidine, slowly dropwise adding ethyl acetate solution of bromopropyne, and placing the ethyl acetate solution in a constant-temperature water bath device, wherein the constant-temperature water bath device comprises a water bath tank, a heat-conducting plate is fixedly connected below the water bath tank, a conical flask is arranged above the heat-conducting plate, the heat-conducting plate is fixedly connected with a heating plate below the heat-conducting plate, a heat-insulating sleeve is fixedly connected outside the water bath tank, the heat-insulating sleeve is fixedly connected above the screw, the screw is movably connected with an adjusting gear, the adjusting gear is movably connected with an upper heat-insulating layer, the solution is removed by reduced pressure distillation at 35 ℃ and is added with dichloromethane and saturated saline solution for extraction and purification, and the dichloromethane organic₁₀H₁₄N, 2-propargyl tetramethylguanidine.

(2) Adding an N, N-dimethylformamide solvent and chitosan into a conical flask, swelling for 6h, adding azidoacetic acid, a catalyst N-hydroxysuccinimide and a condensing agent dicyclohexylcarbodiimide in a mass ratio of 100:5:15:20, reacting at a constant temperature of 50 ℃ in a dark place for 36h, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the azido chitosan.

(3) Adding an N, N-dimethylformamide solvent and chitosan azide into a conical flask, swelling for 12 hours, adding 2-propargyl tetramethylguanidine, a catalyst cuprous bromide and a ligand triethylamine, wherein the mass ratio of the four substances is 100:5:0.035:0.05, reacting at a constant temperature of 30 ℃ for 24 hours under the protection of nitrogen, adding distilled water for precipitation, filtering off the solvent by suction, and washing with distilled water and ethanol to obtain the tetramethylguanidino chitosan.

(4) Adding distilled water, polyvinyl alcohol and tetramethylguanidyl chitosan into a conical flask, stirring for 45min, adding nanocellulose and glycerol serving as a plasticizer, wherein the mass ratio of the nanocellulose to the glycerol is 10:15:100:12, ultrasonically dispersing uniformly, defoaming the solution in vacuum, and naturally casting and curing on a polytetrafluoroethylene plate to obtain the antibacterial chitosan-cellulose biomass composite film.

Adding an agar culture medium and activated escherichia coli suspension bacteria into an aseptic culture dish, adding a cut antibacterial chitosan-cellulose biomass composite film as an experimental group, placing the aseptic culture dish in a constant-temperature constant-humidity incubator by taking the non-added composite film as a blank control, culturing for 24 hours at 37 ℃, observing the colony count, and calculating the bacteriostasis rate, wherein the bacteriostasis rate is (blank colony count-experimental group colony count)/blank group colony count, and the test standard is GB/T20944.1-2007.

Testing	Number of colonies in the test group	Number of blank colonies	Bacteriostatic ratio (%)
				Example 1	5	41	87.8
Example 2	3	41	92.7
				Example 3	2	41	95.1
Example 4	6	41	85.4
				Comparative example 1	19	41	53.7